CN107352815A - Has the product of the scratch-resistant of optical property with a grain of salt - Google Patents
Has the product of the scratch-resistant of optical property with a grain of salt Download PDFInfo
- Publication number
- CN107352815A CN107352815A CN201710547668.1A CN201710547668A CN107352815A CN 107352815 A CN107352815 A CN 107352815A CN 201710547668 A CN201710547668 A CN 201710547668A CN 107352815 A CN107352815 A CN 107352815A
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- film structure
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- Granted
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- 230000003287 optical effect Effects 0.000 title abstract description 36
- 230000003678 scratch resistant effect Effects 0.000 title description 10
- 150000003839 salts Chemical class 0.000 title description 9
- 239000000758 substrate Substances 0.000 claims abstract description 204
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 40
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 169
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- -1 silicon aluminium keto nitride Chemical class 0.000 claims description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 7
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- 230000003014 reinforcing effect Effects 0.000 abstract description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
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- 238000004544 sputter deposition Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- 239000006117 anti-reflective coating Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 2
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- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- 229910052573 porcelain Inorganic materials 0.000 description 2
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- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/3442—Applying energy to the substrate during sputtering using an ion beam
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G02B1/105—
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/90—Other aspects of coatings
- C03C2217/91—Coatings containing at least one layer having a composition gradient through its thickness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
- Y10T428/31612—As silicone, silane or siloxane
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The one or more aspects of the present invention are related to a kind of product, the product includes the optic film structure (220) being arranged in inorganic oxide substrate (110), the inorganic oxide substrate can include can be as amorphous or crystal reinforcing or nonreinforcement base material, so as to which scratch resistance is presented in product and retains optical property that is identical with the inorganic oxide substrate without the optic film structure being disposed above or more improving.In one or more embodiments, 85% or bigger average transparency is presented in the product on visible spectrum (for example, 380nm -780nm).The embodiment of optic film structure (200) includes the oxide containing aluminium, the nitrogen oxides containing aluminium, nitride (such as AlN) containing aluminium and combinations thereof.Optic film structure as described herein also includes the transparent dielectric containing oxide, and the oxide is such as Si oxide, chromium oxide, aluminum oxide and combinations thereof.Additionally provide the method to form this product.
Description
Present patent application is that international application no is PCT/US2014/036873, and international filing date is May 6 in 2014
Day, it is entitled " to have the resistance to of optical property with a grain of salt into the Application No. 201480038941.2 of National Phase in China
The divisional application of the application for a patent for invention of the product of scraping ".
The application requires the U.S. Provisional Application Ser the 61/th that September in 2013 submits on the 13rd according to 35U.S.C. § 119
The priority of 877, No. 568, and the U.S. Provisional Application Ser the 61/820th, 407 submitted on May 7th, 2013 are preferential
Power, the content of above-mentioned application are the bases of the application and by reference to being intactly hereby incorporated by.
Background
The present invention relates to for display coversheet glass applications, there is the system of the optical property of scratch resistance and reservation
Product, it particularly relates to include the product of the optic film structure with scratch resistance, wherein the product is presented on visible spectrum
85% or bigger average transmittance.As used herein, term " visible spectrum " includes about 380nm- about 780nm wavelength.
Cover-plate glass product is frequently utilized for protecting the key device in electronic product, is used for inputting and/or showing for providing
Show and/or the user interface of many other functions.This product includes mobile device such as smart mobile phone, Mp 3 player peace
Plate computer.These applications often require that scratch resistance and are related to the stronger optical of maximum transmission rate and minimal reflection ratio
Can feature.In addition, cover-plate glass application requirement is presented or observed in a manner of reflecting and/or transmiting when viewing angle changes
To color do not significantly change.Because if the change of significance degree, product occur with viewing angle for reflection or transmission
User by the color for perceiving display or the change of brightness, this can reduce the quality for the display observed.
After use under severe operating conditions, scraping is usually presented in existing cover-plate glass product.Evidence shows in list
Damage caused by the sharp contact occurred in one event is the master of visible scraping in cover-plate glass product used in mobile device
Want source.Once occurring significant scraping on cover-plate glass product, the outward appearance of product can deteriorate, because scraping causes light scattering to increase
Add, this can cause the brightness of the image on display, definition and contrast to significantly reduce.Significant scraping can also influence touch-sensitive
The accuracy and reliability of display.Therefore, it is ugly that these, which scrape even more inapparent scrape, and can influence product
Performance.
Single incident scrapes damage and can compared with abrasion damage.Cover-plate glass does not suffer from abrasion damage generally, because rubbing
Damage damage to surface object (such as sand, rubble and sand paper) from hard generally by reciprocatingly sliding contact to produce.On the contrary,
Generally only experience contacts cover-plate glass product with reciprocatingly sliding for soft object such as finger.In addition, abrasion damage can produce heat,
Chemical bond in this degradable membrane material, cause product that thin slice stripping or other types of damage occurs.In addition, because abrasion is damaged
The time of the period of the bad experience usually single incident than causing to scrape is longer, and the membrane material of experience abrasion damage can also occur
Oxidation, this further reduces the durability of film and resulting product.The single incident for causing to scrape generally is not related to and caused abrasion
The event identical situation of damage, therefore the solution for being usually used to prevent abrasion from damaging can not prevent the scraping in product.
Furthermore it is known that scraping and abrasion damage solution usually reduce optical property.
Therefore, this area needs that scratch resistance and the manufacturer of the new product of favorable optical performance and the product is presented
Method.
General introduction
The first aspect of the present invention is related to a kind of product, and the product is included with opposite major surfaces and conversely secondary
The inorganic oxide substrate on surface and it is arranged at least one in the opposite major surfaces of the inorganic oxide substrate
Optic film structure.According to the product of one or more embodiments, (such as 380nm -780nm) is presented on visible spectrum
85% or bigger average transmittance.In a specific embodiment, product present total reflection ratio (its include specular reflectance and
Diffusing reflection ratio) it is equal to or less than the total reflection ratio of the inorganic oxide substrate without the optic film structure being disposed above.One
Kind or the products of numerous embodiments that substantially flat transparency spectrum (or reflectance spectra) or transparency is presented is (or anti-
Penetrate ratio) it is substantial constant on visible spectrum.Product can also be in (L, a*,b*) color is presented in colorimetric system, so as to transparent
Degree color or the distance of reflectivity coordinate and reference point are approximately less than 2.In one or more embodiments, reference point can be L*a*
b*Color space (or color coordinates a*=0, b*=0) color of origin (origin) (0,0) or inorganic oxide substrate in
Coordinate.
In one or more embodiments, inorganic oxide substrate can include amorphous base material, crystal substrate or its group
Close.In the embodiment using amorphous base material, amorphous base material can include glass baseplate, and the glass baseplate can be what is strengthened
Or nonreinforcement.The example of amorphous base material includes soda-lime glass, alkali alumino-silicates glass, the borosilicate glass containing alkali
And/or alkaline Boroalumino silicate glasses.The example of crystal substrate includes the glass-ceramic substrates strengthened, the glass ceramics of nonreinforcement
Base material, single crystal substrate (such as single-crystal substrate such as sapphire) or its combination.
According to one or more embodiments, optic film structure assigns product with scratch resistance.Such as passed through this paper institutes
Measured by strange (Berkovitch) pressure head test of diamond problem about Bellco haemodialysis dimension stated, optic film structure can be at least comprising hardness
16Gpa at least one layer,.In other embodiments, when close to carbonization silicon ball to surface measurement when, optic film structure present
Coefficient of friction be smaller than 0.3.
Optic film structure can include siliceous oxide, siliceous nitride, containing aluminium nitride (such as AlN and
AlxSiyN), (such as the AlO of the nitrogen oxides containing aluminiumxNyAnd SiuAlvOxNy), containing the oxide of aluminium or its combination.In some implementations
In mode, optic film structure includes transparent dielectric material, such as SiO2、GeO2、Al2O3、Nb2O5、TiO2、Y2O3With other classes
Like material and combinations thereof.The optic film structure of one or more embodiments can have layer structure, or specifically have extremely
Few two layers (for example, first layer and second layer), so as to which first layer is arranged between inorganic oxide substrate and the second layer.
In one or more embodiments, the first layer of optic film structure can include siliceous oxide, siliceous nitrogen
Compound, the oxide containing aluminium, nitrogen oxides (such as the AlOxNy and Si containing aluminiumuAlvOxNy), nitride containing aluminium (such as
AlN and AlxSiyN) or its combination.Specifically, first layer can include Al2O3,AlN,AlOxNyOr its combination.Selected in another kind
Xiang Zhong, first layer can also include transparent dielectric material, such as SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With it is other similar
Material and combinations thereof.
In the embodiment that wherein optic film structure includes AlN or AlOxNy, AlN or AlOxNy can include amorphous knot
Structure, microstructure or its combination.Additional or optional, AlN or AlOxNy can include polycrystalline structure.
In one or more embodiments, optic film structure can combine one or more modifying agent.Or optical film knot
Structure can be free of modifying agent.In one or more embodiments, at least one modifying agent can be combined into and utilize AlN's
Optic film structure.In this embodiment, AlN can be adulterated with least one modifying agent or forms alloy with AlN.It is exemplary to change
Property agent includes BN, Ag, Cr, Mg, C and Ca.In a kind of variant, conduction property is presented in optic film structure.In this embodiment
In, optic film structure can combine modifying agent, and Mg and/or Ca is included in the modifying agent.
The first layer of optic film structure can include the first sublayer and the second sublayer.In this embodiment, the first sublayer
It may be provided between the second sublayer and inorganic oxide substrate.In a kind of variant, the first sublayer can include Al2O3, the second sublayer
AlN can be included.
In one or more embodiments, the first sublayer can include AlOxNy, the second sublayer can include AlN.In another kind
In variant, first layer includes 3 sublayers (such as the first sublayer, the second sublayer and the 3rd sublayer).In this embodiment,
First sublayer and the 3rd sublayer can include AlN, and the second sublayer can include transparent dielectric material such as SiO2,GeO2,Al2O3,
Nb2O5,TiO2,Y2O3With other similar materials and combinations thereof.
In one or more embodiments, the first layer of optic film structure can include composition gradient.The composition gradient can
Include oxygen content gradient, nitrogen content gradient, silicone content gradient and/or aluminium content gradient.In one or more embodiments, group
Can include silicon/aluminium composition gradient into gradient, wherein thickness of the atom % of silicon and aluminium along first layer change independently of one another or
Change related to each other.In other embodiments, composition gradient can include oxygen/nitrogen composition gradient, wherein oxygen and nitrogen
Thickness of the atom % along first layer changes or changed related to each other independently of one another.
In a specific embodiment, the oxygen content of first layer and/or silicone content can be away from inorganic oxide substrates
Thickness of the direction along first layer reduces.In another embodiment, aluminium and/or nitrogen content gradient can be away from inorganic oxygen
Thickness increase of the direction of compound base material along first layer.In one or more embodiments, first layer can include oxygen content ladder
Spend and include AlN.In this embodiment, the first layer of the neighbouring second layer can be free of oxygen.In a particular embodiment, first layer
In thickness of the composition gradient along first layer be constant.In other specific embodiments, the composition gradient edge in first layer
The thickness for first layer is not constant.In other more specific embodiments, composition gradient in first layer is along first layer
Thickness is stepping form, and progressively the composition gradient of form can be constant or non-constant.
According to one or more embodiments, first layer includes refractive index gradient.The refractive index of first layer can be along first
The thickness of layer is increased or decreased or is otherwise changed, so as to improve optic film structure and/or product as described herein
Optical property.
In one or more embodiments, the second layer of optic film structure includes transparent dielectric material, such as SiO2,
GeO2,Al2O3,Nb2O5,TiO2,Y2O3With other similar materials and combinations thereof.
Optionally, optic film structure can include the extra film or layer being arranged on the second layer of optic film structure.One
In kind variant, product can include the film of parcel.The one or more that the film of parcel may be provided at inorganic oxide substrate is opposite
In minor surface and/or one or more opposite major surfaces.The film wrapped up wherein is arranged on inorganic oxide substrate
In embodiment on one or more opposite major surfaces, the film of parcel may be provided at inorganic oxide substrate and optical film
Between structure.The film of parcel can also form a part (such as first sublayer of optic film structure) for optic film structure.
Product optionally includes passivating film or intermediate layer.In one or more embodiments, intermediate layer may be provided at
Between optic film structure and inorganic oxide substrate.In one or more alternate embodiments, intermediate layer can be optical film knot
A part for structure.Such as one or more embodiments, intermediate layer can form the first layer or first sublayer of optic film structure
Part.
In one or more embodiments, the thickness of optic film structure can be at least about 1 μm or at least about 2 μm.Work as light
When membrane structure includes layer structure, the thickness of first layer can be more than the thickness of the second layer of optic film structure.
The second aspect of the present invention is related to the method to form product as described herein.In one or more embodiments
In, methods described, which includes, provides inorganic oxide substrate (as provided elsewhere herein), and in about 0.5 millitorr-about 10
Low stress optic film structure is set under the pressure of millitorr in inorganic oxide substrate.At least 16Gpa can be presented in optic film structure
Hardness.Optic film structure can layer structure as described herein.
In one or more embodiments, methods described is included using evaporating deposition technique come in inorganic oxide substrate
Upper setting optic film structure.Evaporating deposition technique can include chemical vapor deposition, physical vapour deposition (PVD), thermal evaporation and/or atom
Layer deposition.In one or more embodiments, methods described is also comprising for example by using modifying agent doping optical membrane structure,
To increase the electrical conductivity of optic film structure.The exemplary modifying agent that can be used to increase the electrical conductivity of optic film structure includes Mg, Ca
And combinations thereof.One or more embodiments of methods described can include the lubricity of increase optic film structure.It is being embodied
In mode, the lubricity for increasing optic film structure includes BN being combined into optic film structure.In one or more embodiments
In, this method can include the stress for reducing optic film structure.In a specific embodiment, this method can include by by BN, Ag,
Cr or its one or more in combining are combined into optic film structure, to reduce the stress of optic film structure.
According to one or more embodiments, this method can include oxygen and/or nitrogen introducing optic film structure.Implement one
In example, this method, which may be optionally contained in, builds oxygen content gradient and/or nitrogen content gradient in optic film structure.In a kind of variant
In, oxygen content gradient includes thickness of the oxygen content along the direction away from inorganic oxide substrate along optic film structure and reduced.
In a kind of variant, nitrogen content gradient includes direction of the nitrogen content along remote inorganic oxide substrate along optic film structure
Thickness increase.This method can also include structure silicone content gradient and/or aluminium content gradient.In one or more embodiments,
This method can include and deposit to one or more source materials (such as silicon and/or aluminium) in inorganic oxide substrate to form light
Membrane structure is learned, and changes one or more processing conditions and be for example fed to the power of one or more source materials to come in optical film knot
Silicone content gradient and/or aluminium content gradient are built in structure.In one or more embodiments, this method is included in optical film knot
Intermediate layer is set between structure and inorganic oxide substrate, or intermediate layer is combined into optic film structure.
Other features and advantages of the present invention, Partial Feature and advantage pair therein are proposed in the following detailed description
For those skilled in the art, it is easy for finding out according to being described, or by implementing to include described in detail below, right
Various embodiments described herein including claim and accompanying drawing and be realized.
It should be understood that what foregoing general description and the following detailed description were all merely exemplary, for providing understanding
The property of claim and the overview of characteristic or framework.Appended accompanying drawing provides a further understanding of the present invention, accompanying drawing
It is incorporated in the present specification a part for simultaneously constitution instruction.One or more embodiments of the present invention have been illustrated,
And it is used for explaining principle and the operation of various embodiments together with specification.
Brief Description Of Drawings
Fig. 1 shows the product according to one or more embodiments.
Fig. 2 shows the product according to one or more embodiments.
Fig. 3 shows the product according to one or more embodiments.
Fig. 4 shows the product according to one or more embodiments.
Fig. 4 A show the embodiment of product shown in Fig. 4.
Fig. 5 shows the product according to one or more embodiments.
Fig. 5 A show the embodiment of product shown in Fig. 5.
Fig. 6 A are the oxygen of the product shown in Figure 4 and 5 or the picture of silicone content.
Fig. 6 B are the nitrogen of the product shown in Figure 4 and 5 or the picture of aluminium content.
Fig. 7 figure shows the relation between the thickness of the optic film structure of Fig. 2 product and refractive index.
Fig. 8 figure shows the relation between the thickness of the optic film structure of Fig. 3 product and refractive index.
Fig. 9 figure shows the relation between the thickness of the optic film structure of Fig. 4 product and refractive index.
Figure 10 A figure shows the relation between the thickness of the optic film structure of Fig. 5 product and refractive index.
Figure 10 B figure shows thickness and the refraction of the optic film structure of the product according to one or more alternate embodiments
Relation between rate.
Figure 11 is contour map, and it shows the color clarity of the optic film structure according to embodiment 1.
Figure 12 is contour map, and it shows the color clarity of the optic film structure according to embodiment 2.
Figure 13 is contour map, and it shows the color clarity of the optic film structure according to embodiment 3.
Figure 14 is contour map, and it shows the color clarity of the optic film structure according to embodiment 4.
Figure 15 is contour map, and it shows the color clarity of the optic film structure according to embodiment 5.
Figure 16 is contour map, and it shows the color clarity of the optic film structure according to embodiment 6.
Figure 17 is contour map, and it shows the color clarity of the optic film structure according to embodiment 7.
Figure 18 is contour map, and it shows the color clarity of the optic film structure according to embodiment 8.
Figure 19 A are the brightness L represented with transparency for embodiment 1*Contour map.
Figure 19 B chart shows the particular color represented with transparency the point (a for embodiment 1*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 19 C chart shows the particular color represented with transparency the point (a for embodiment 1*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 20 A are the brightness L represented with transparency for embodiment 2*Contour map.
Figure 20 B chart shows the particular color represented with transparency the point (a for embodiment 2*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 20 C chart shows the particular color represented with transparency the point (a for embodiment 2*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 21 A are the brightness L represented with transparency for embodiment 3*Contour map.
Figure 21 B chart shows the particular color represented with transparency the point (a for embodiment 3*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 21 C chart shows the particular color represented with transparency the point (a for embodiment 3*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 22 A are the brightness L represented with transparency for embodiment 4*Contour map.
Figure 22 B chart shows the particular color represented with transparency the point (a for embodiment 4*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 22 C chart shows the particular color represented with transparency the point (a for embodiment 4*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 23 A are the brightness L represented with transparency for embodiment 5*Contour map.
Figure 23 B chart shows the particular color represented with transparency the point (a for embodiment 5*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 23 C chart shows the particular color represented with transparency the point (a for embodiment 5*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 24 A are the brightness L represented with transparency for embodiment 6*Contour map.
Figure 24 B chart shows the particular color represented with transparency the point (a for embodiment 6*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 24 C chart shows the particular color represented with transparency the point (a for embodiment 6*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 25 A are the brightness L represented with transparency for embodiment 7*Contour map.
Figure 25 B chart shows the particular color represented with transparency the point (a for embodiment 7*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 25 C chart shows the particular color represented with transparency the point (a for embodiment 7*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 26 A are the brightness L represented with transparency for embodiment 8*Contour map.
Figure 26 B chart shows the particular color represented with transparency the point (a for embodiment 8*,b*) distance d, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 26 C chart shows the particular color represented with transparency the point (a for embodiment 8*,b*) log10D, should
Particular color point (a*,b*) correspond to such as by L*a*b*The SiO shown in reference axis in color space apart from origin (0,0)2
And Al2O3Film thickness.
Figure 27 shows the reflectivity % on visible spectrum according to the layer of one or more embodiments.
Figure 28 shows the transparency % on visible spectrum according to the layer of one or more embodiments.
Figure 29 A are a represented with reflectivity of the optic film structure for embodiment 11*Contour map.
Figure 29 B are a represented with reflectivity of the optic film structure and base material for embodiment 11*Contour map.
Figure 29 C are the b represented with reflectivity of the optic film structure and base material for embodiment 11*Contour map.
Figure 29 D are the b represented with reflectivity of the optic film structure and base material for embodiment 11*Contour map.
Figure 29 E be for embodiment 11 optic film structure and base material with reflectivity represent in L*a*b*Color space
Middle a*And b*Apart from the contour map of the distance of origin (0,0).
Figure 29 F are a represented with reflectivity for optic film structure and base material*And b*Apart from the color coordinates of base material
The contour map of distance.
Figure 30 A are a represented with transparency of the optic film structure for embodiment 11*Contour map.
Figure 30 B are a represented with transparency of the optic film structure and base material for embodiment 11*Contour map.
Figure 30 C are the b represented with transparency of the optic film structure for embodiment 11*Contour map.
Figure 30 D are the b represented with transparency of the optic film structure and base material for embodiment 11*Contour map.
Figure 30 E be for embodiment 11 optic film structure and base material with transparency represent in L*a*b*Color space
Middle a*And b*Apart from the contour map of the distance of origin (0,0).
Figure 30 F are a represented with transparency for optic film structure and base material*And b*Apart from the color coordinates of base material
The contour map of distance.
It is described in detail
It is shown in the drawings in detail below with reference to the various embodiments of the present invention, the example of these embodiments.As long as
It is possible to, makes same or similar part is denoted by the same reference numerals in all of the figs.
With reference to figure 1, the first aspect of the present invention is related to product 100, and it is included with the main opposite He of side 112,114
The inorganic oxide substrate 110 of opposite secondary side 116,118, and it is arranged on a phase of inorganic oxide substrate 110
Optic film structure 120 on anti-primary side 112.In addition to being arranged on opposite primary side 112 or conduct is replaced
In generation, optic film structure can be arranged on another opposite primary side 114 and/or opposite secondary side 116,118
On one or two.
When applied to optic film structure as described herein, term " film " may include one formed by any known process
Individual or multiple layers, including discrete deposition or continuous deposition process.These layers mutually can be contacted directly.The layer can be by identical
Material or more than one different materials formed.In one or more of alternate embodiments, these layers may include at it
Between the intermediate layer of different materials that sets.In one or more embodiments, the film may include one or more of continuous
With continual layer and/or it is one or more of discontinuously and the layer of interruption (that is, mutually adjacent formation has a different materials
Layer).
As used herein, term " setting " coats material, deposits and/or formed including the use of any known process arrives
On surface.The material of setting can construct layer or film as herein defined.Phrase " being arranged on " includes material to be formed to surface
Upper situation about directly being contacted with surface so as to material, and also include wherein forming material on the surface and wherein in the material of setting
One or more of intermediate materials between surface be present.Intermediate materials can construct layer or film as herein defined.
According to one or more embodiments, it is average transparent that product 100 is presented 85% or bigger on visible spectrum
Degree.In one or more embodiments, the total reflection ratio of product 100 is 15% or smaller.As used herein, term is " saturating
Lightness " be defined as in the range of setted wavelength by material (such as product, inorganic oxide substrate or optic film structure or it
Part) transmission incident optical power percentage.As used herein, term " reflectivity " is similarly defined as given
From the incidence of material (such as product, inorganic oxide substrate or optic film structure or their part) reflection in wave-length coverage
The percentage of luminous power.Transparency and reflectivity are determined using specific line width.In one or more embodiments, characterize
The spectral resolution of transparency and reflectivity is less than 5nm or 0.02eV.
In one or more specific embodiments, following average transparencies can be presented in product 100 on visible spectrum：About
85% or bigger, about 85.5% or bigger, about 86% or bigger, about 86.5% or bigger, about 87% or bigger, about 87.5% or
It is bigger, about 88% or bigger, about 88.5% or bigger, about 89% or bigger, about 89.5% or bigger, about 90% or bigger, about
90.5% or bigger, about 91% or bigger, about 91.5% or bigger, about 92% or bigger, about 92.5% or bigger, about 93% or
It is bigger, about 93.5% or bigger, about 94% or bigger, about 94.5% or bigger, about 95% or bigger, about 96% or bigger, about
97% or bigger, about 98% or bigger, or about 99% or bigger.In one or more of the other embodiment, product it is total anti-
Penetrate than can be about 15% or smaller, about 14% or smaller, about 13% or smaller, about 12% or smaller, about 11% or smaller, about
10% or smaller, about 9% or smaller, about 8% or smaller, about 7% or smaller, or about 6% or smaller.In some specific implementations
In mode, the total reflection ratio of product is about 6.8% or smaller, about 6.6% or smaller, about 6.4% or smaller, about 6.2% or more
It is small, about 6% or smaller, about 5.8% or smaller, about 5.6% or smaller, about 5.4% or smaller, about 5.2% or smaller, about 5%
Or it is smaller, about 4.8% or smaller, about 4.6% or smaller, about 4.4% or smaller, about 4.2% or smaller, about 4% or smaller, about
3.8% or smaller, about 3.6% or smaller, about 3.4% or smaller, about 3.2% or smaller, about 3% or smaller, about 2.8% or more
It is small, about 2.6% or smaller, about 2.4% or smaller, about 2.2% or smaller, about 2% or smaller, about 2.8% or smaller, about
2.6% or smaller, about 2.4% or smaller, about 2.2% or smaller, about 2% or smaller, about 1.8% or smaller, about 1.6% or more
It is small, about 1.4% or smaller, about 1.2% or smaller, about 1% or smaller, or about 0.5% or smaller.Implemented according to one or more
Mode, the total reflection of product 100 is than the total reflection ratio equal to or less than inorganic oxide substrate 110.In other embodiments,
The total reflection of product is less than about 20%, or 10% than the total reflection with inorganic oxide substrate than differing.
According to one or more embodiments, 85% or bigger average transmittance is presented in product 100 on visible spectrum
Rate.Term " light transmittance " refers to the amount of the light transmitted by medium.The measurement of light transmittance is incident light on medium and leaves Jie
Ratio between the amount of the light (it is not by dieletric reflection or absorption) of matter.In other words, light transmittance is both not anti-by medium
Penetrate and not by the part of the incident light of Absorption of Medium.Term " average transmittance " refers to the light transmittance that is multiplied by luminous efficiency function
Spectrum mean value, described by CIE standard sight persons.Following average transmittances can be presented in product 100 on visible spectrum：85% or
It is bigger, 85.5% or bigger, 86% or bigger, 86.5% or bigger, 87% or bigger, 87.5% or bigger, 88% or bigger,
88.5% or bigger, 89% or bigger, 89.5% or bigger, 90% or bigger, 90.5% or bigger, 91% or bigger,
91.5% or bigger, 92% or bigger, 92.5% or bigger, 93% or bigger, 93.5% or bigger, 94% or bigger,
94.5% or bigger, or 95% or bigger.
Product 100 includes preceding surface 101 and optical property, so as to work as from preceding surface to be seen different from the angle of normal incidence
When seeing product, product does not provide reflectivity tone, or the reflectivity tone provided is neutral or colourless.In other words, from except
During angle viewing beyond directly before the preceding surface 101, reflection is colourless.It is additional or optional, even if viewing angle
Degree change, from color substantially constantization of product reflection.In one or more embodiments, enter in the normal direction of the light of transmission
When penetrating, product is in (L, a*,b*) color clarity and/or reflectivity, and the color coordinates of distance reference point are presented in colorimetric system
Distance is approximately less than 2.In one or more embodiments, reference point can be color coordinates a*=0, b*=0, or reference point can be
The color coordinates of inorganic oxide substrate 110.In one or more embodiments, transparency and/or reflectivity color
Coordinate distance is smaller than 1 or even less than 0.5.In one or more embodiments, transparency and/or reflectivity color
Coordinate distance can be 1.8,1.6,1.4,1.2,0.8,0.6,0.4,0.2,0 and all scopes between them and sub- model
Enclose.When reference point is color coordinates a*=0, b*When=0, color coordinates distance is calculated by following formula, When reference point is the color coordinates of inorganic oxide substrate 110, color coordinates distance passes through following public affairs
Formula calculates,
Inorganic oxide substrate
As Figure 1-5, inorganic oxide substrate 110 include be arranged at least one opposite major surfaces (112,
114) the optical film system 120,220,320,420,520 on.Inorganic oxide substrate 110 includes minor surface 116,118, its
It can include or not comprising the film or material being disposed above.Inorganic oxide substrate 110 can include amorphous base material, crystal base
Material or its combination.In one or more embodiments, amorphous base material can include glass baseplate, and it can be strengthening or non-strong
Change.The example of suitable glass baseplate includes soda-lime glass base material, alkali alumino-silicates glass baseplate, the borosilicate containing alkali
Glass baseplate and alkaline Boroalumino silicate glasses base material.In some variants, glass baseplate can be free of lithia.A kind of or more
In kind alternate embodiments, inorganic oxide substrate 110 can include crystal substrate such as glass-ceramic substrates, and (it can be to strengthen
Or nonreinforcement) or can include mono-crystalline structures, such as sapphire.In one or more embodiments, inorganic oxide
Thing base material 110 include amorphous substrate (such as glass) and crystal coating (such as sapphire layer, polycrystal alumina layer and/
Or spinelle (MgAl2O4) layer).
Inorganic oxide substrate 110 can be substantially flat plate, but other embodiment can utilize bending or with it
The inorganic oxide substrate that its mode shapes or carved.Inorganic oxide substrate 110 can be that substantially optics is colourless, transparent and nothing
Light scattering.The refractive index of inorganic oxide substrate 110 can be about 1.45- about 1.55.Such as in the one or more of this base material
Measured on main opposite surface 112,114, inorganic oxide substrate 110 may be characterized as having high average flexural strength (such as
Described herein, when compared with the inorganic oxide substrate of no reinforcing) or high surface failure strain (it is as described herein, when with
When the inorganic oxide substrate do not strengthened is compared).
Additional or optional, for aesthetically and/or functionally reason, the thickness of inorganic oxide substrate 110 can be along it
One or more dimension variations.For example, compared with the region closer to center of inorganic oxide substrate 110, inorganic oxide
The edge of thing base material 110 can be thicker.Length, width and the thickness size of inorganic oxide substrate 110 also can be according to product applications
Or purposes change.
Various distinct methods can be used to provide inorganic oxide substrate 110.Such as when inorganic substrate 110 includes glass
During base material, the example of glass baseplate forming method includes float glass technology, and glass tube down-drawing for example fuses drawing and slit
Drawing.
The glass baseplate prepared by float glass technology can have smooth surface and uniform thickness, and it passes through the gold in melting
Float the glass of melting on the bed of category (be typically tin) to prepare.In an example process, melten glass is fed to molten
Melt on tin bed surface, form float glass band.When glass tape flows along tin bath, temperature is gradually decrease until that glass tape solidifies
Cheng Kecong tin is raised to the solid glass base material on roller.Once leaving bath, further glass baseplate can be cooled down and annealed
To reduce internal stress.
Glass baseplate prepared by glass tube down-drawing has uniform thickness, and it has relatively intact surface.Because glass baseplate
Average flexural strength is by the amount of surface blemish and controlling for size, therefore the intact surface of exposure level minimum is with higher
Initial strength.When then carrying out further strengthening (such as chemical enhanced) to the high strength glass base material, the intensity of gained
The intensity that surface had carried out polishing and the glass baseplate polished can be higher than.The glass baseplate that glass tube down-drawing manufactures can be pulled to
Thickness is approximately less than 2 millimeters.In addition, glass tube down-drawing glass baseplate has the surface of very flat-satin, can grinding without high cost
Mill and polishing are just used for final application.
The fusion drawing includes groove using drawing container, such as the drawing container, for receiving the glass of melting
Raw material.Length of these grooves along groove, there is the weir of open-top in groove both sides.When loading melted material in groove
When, the glass of melting is from weir overflow.Under gravity, melten glass as the glass-films of two flowings from drawing
The outer surface of container flows down.These draw containers downwardly and extend internally so that they draw container below
Edge combines.The glass-film of two flowings combines in the edge, so as to fuse and be formed single flowing glass baseplate.It is described
The advantages of fusing drawing is, due to that can be fused together from two pieces of glass-films of groove overflow, therefore obtained glass base
Any outer surface of material is not all in contact with any part of equipment.Therefore, fuse the surface nature of the glass baseplate of drawing
Do not influenceed by this contact.
Slot draw is different from fusion drawing.In slot draw, the glass raw material of melting is provided to drawing
Container.The bottom for drawing container has open slit, and the open slots have what the length along slit extended
Nozzle.The glass of melting flows through the slit/nozzle, is pulled down in the form of continuous base material by the slit/nozzle, and enter
Annealed zone.
In some embodiments, being selected from the group for 0-2 moles of % can be included in glass baseplate composition therefor dispensing
At least one fining agent：Na2SO4、NaCl、NaF、NaBr、K2SO4, KCl, KF, KBr and SnO2。
Once formed, can strengthened glass base material, to form the glass baseplate of reinforcing.It is noted that also it can be used and glass base
Material identical mode strengthened glass ceramic base material.As used herein, term " base material strengthened " can refer to by chemical enhanced
Glass baseplate or glass-ceramic substrates, for example, by using in larger ion and glass or glass-ceramic substrates surface it is less from
Son carries out ion exchange, chemical enhanced so as to carry out.But other intensifying methods well known to usable the art are for example
Heat tempering carrys out strengthened glass base material.
The base material of reinforcing as described herein can be carried out chemical enhanced by ion exchange process.In ion exchange process,
Glass or glass-ceramic substrates are generally submerged into a predetermined time segment in molten salt bath, on glass or glass-ceramic substrates surface
Or the ion of near surface exchanges with the larger metal ion in salt bath.In one embodiment, the fuse salt
The temperature of bath is about 400-430 DEG C, and the predetermined time is about 4-8 hours.Larger ions binding is entered glass or glass is made pottery
Porcelain base material in the region close to surface or forming compression stress in the region with adjacent base material surface by strengthening
Base material.Corresponding tensile stress is induced in middle section or the apart region of substrate surface certain distance to answer to balance compression
Power.Chemical enhanced glass or glass pottery can be described more specifically as using the glass or glass-ceramic substrates of this strengthening process
The glass or glass-ceramic substrates of porcelain base material or ion exchange.
In one example, the sodium ion in the glass or glass-ceramic substrates of reinforcing can be by from molten salt bath (such as nitre
Acid potassium salt is bathed) in potassium ion replace, but also may be used with other alkali metal ions (such as rubidium or caesium) of larger atomic radius
To replace the less alkali metal ion in glass.According in embodiment, less alkali is golden in glass or glass ceramics
Category ion can be replaced by Ag+.Similar, other alkali metal salts, such as, but not limited to sulfate, phosphate, halide etc. can
For the ion exchange process.
Less ion is replaced with larger ion at a temperature of the temperature that can be relaxed less than glass network, chemical strong
The whole surface of the base material of change produces ion distribution, and it produces stress curve.The larger volume of the ion of entrance is on the surface
Compression stress (CS) is produced, tension force (center tension, or CT) is produced in the substrate center of reinforcing.Compression stress and center tension
Relation be shown below:
Wherein t is the gross thickness for the glass or glass-ceramic substrates strengthened, and compression layer depth (DOL) is to exchange depth.Hand over
Change within glass or glass-ceramic substrates that depth can be described as strengthening depth (that is, from the surface of glass base ability to glass or
The distance of glass-ceramic substrates middle section), progress ion exchange is promoted by ion exchange process in the depth.
In one embodiment, the surface compression stress of the glass of reinforcing or glass-ceramic substrates can be 300MPa or more
Greatly, such as, 400MPa or bigger, 450MPa or bigger, 500MPa or bigger, 550MPa or bigger, 600MPa or bigger,
650MPa or bigger, 700MPa or bigger, 750MPa or bigger or 800MPa or bigger.The glass or glass-ceramic substrates of reinforcing
Compression layer depth can be 15 μm or bigger, 20 μm or bigger (such as 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or more
Greatly) and/or central tension can be 10MPa or bigger, 20MPa or bigger, 30MPa or bigger, 40MPa or more it is big (such as
42MPa, 45MPa, or 50MPa or bigger) but less than 100MPa (such as 95,90,85,80,75,70,65,60,55MPa or more
It is small).In one or more of embodiments, the glass or glass-ceramic substrates of reinforcing have following one or more
Kind:Surface compression stress is more than 500MPa, and compression layer depth is more than 15 μm, and central tension is more than 18MPa.
Although it is not intended to be limited to theory, it is believed that surface compression stress is more than 500MPa and compression layer depth is greater than about 15 μm
Generally there is glass or glass-ceramic substrates than nonreinforcement (or in other words, not to have for the glass or glass-ceramic substrates of reinforcing
The glass baseplate for having by ion exchange or otherwise strengthening) bigger failure strain.
Example available for the glass of inorganic oxide substrate may include alkali alumino-silicates glass composition or alkaline boron
Alumina silicate glass composition, but it is envisioned that other glass compositions.The feature of these glass compositions can be can ion friendship
Change." ion exchangeable " used herein refers to the base material with following characteristic：It is included can be with size more greatly or more
Small same valence state cation exchange is located at the composition of the cation at or near substrate surface.A kind of exemplary glass component includes
SiO2、B2O3And Na2O, wherein, (SiO2+B2O3) >=66 mole %, and Na2O >=9 mole %.In one embodiment, glass
Glass composition includes at least 6 weight % aluminum oxide.In other embodiments, the glass group that inorganic oxide substrate includes
Into comprising one or more alkaline earth oxides, it is at least 5 weight % so as to the content of alkaline earth oxide.In some realities
Apply in mode, suitable glass composition also includes K2O, at least one of MgO and CaO.In a specific embodiment, it is inorganic
Glass composition used can include 61-75 moles of %SiO in oxide base material2；7-15 moles of %Al2O3；0-12 moles of %
B2O3；9-21 moles of %Na2O；0-4 moles of %K2O；0-7 moles of %MgO；With 0-3 moles of %CaO.
Included suitable for the other examples glass composition of inorganic oxide substrate：60-70 moles of %SiO2；6-14 rubs
You are %Al2O3；0-15 moles of %B2O3；0-15 moles of %Li2O；0-20 moles of %Na2O；0-10 moles of %K2O；0-8 moles of %
MgO；0-10 moles of %CaO；0-5 moles of %ZrO2；0-1 moles of %SnO2；0-1 moles of %CeO2；Less than 50ppmAs2O3；With it is small
In 50ppmSb2O3；Wherein 12 moles of %≤(Li2O+Na2O+K2O)≤20 mole % and 0 mole of %≤(MgO+CaO)≤10 are rubbed
You are %.
Included suitable for the another exemplary glass composition of inorganic oxide substrate：63.5-66.5 mole %SiO2；8-12
Mole %Al2O3；0-3 moles of %B2O3；0-5 moles of %Li2O；8-18 moles of %Na2O；0-5 moles of %K2O；1-7 moles of %
MgO；0-2.5 moles of %CaO；0-3 moles of %ZrO2；0.05-0.25 moles of %SnO2；0.05-0.5 moles of %CeO2；It is less than
50ppmAs2O3；With less than 50ppmSb2O3；Wherein 14 moles of %≤(Li2O+Na2O+K2O)≤18 mole % and 2 mole of %≤
(MgO+CaO)≤7 mole %.
In a specific embodiment, oxidation is included suitable for the alkali alumino-silicates glass composition of inorganic oxide substrate
Aluminium, at least one alkali metal and the SiO for being more than 50 moles of % in some embodiments2, in other embodiments at least
For 58 moles of % SiO2, and it is at least 60 moles of % SiO in other embodiments again2, wherein ratioWherein the ratio of component is in terms of mole % and modifying agent is alkali metal oxide.In a specific embodiment,
This glass composition includes:58-72 moles of %SiO2, 9-17 moles of %Al2O3, 2-12 moles of %B2O3, 8-16 moles of %
Na2O, and 0-4 moles of %K2O, wherein ratio
Again in another embodiment, inorganic oxide substrate can include alkali alumino-silicates glass composition, and it is wrapped
Contain:64-68 moles of %SiO2；12-16 moles of %Na2O；8-12 moles of %Al2O3；0-3 moles of %B2O3；2-5 moles of %K2O；
4-6 moles of %MgO；With 0-5 moles of %CaO, wherein：66 moles of %≤SiO2+B2O3+ CaO≤69 mole %；Na2O+K2O+
B2O3+MgO+CaO+SrO>10 moles of %；5 moles of %≤MgO+CaO+SrO≤8 mole %；(Na2O+B2O3)-Al2O3≤ 2 rub
You are %；2 moles of %≤Na2O-Al2O3≤ 6 moles of %；With 4 moles of %≤(Na2O+K2O)-Al2O3≤ 10 moles of %.
In an alternative embodiment, inorganic oxide substrate can include alkali alumino-silicates glass composition, and it is included:2
Mole % or more Al2O3And/or ZrO2, or 4 moles of % or more Al2O3And/or ZrO2。
When inorganic oxide substrate 110 includes crystal substrate, base material can include monocrystalline, and it can include Al2O3.This list
Brilliant base material is referred to as sapphire.Other materials suitable for crystal substrate include polycrystal alumina layer and/or spinelle (MgAl2O4)。
Optionally, crystal substrate 100 can include glass-ceramic substrates, and it can be strengthening or nonreinforcement.Suitable glass
The example of glass ceramics can include Li2O-Al2O3-SiO2System (i.e. LAS- systems) glass ceramics, MgO-Al2O3-SiO2System is (i.e.
MAS- systems) glass ceramics and/or the glass ceramics of predominant crystal phase is included, the crystal phase includes β-quartz solid solution, β-lithium
Pyroxene ss, cordierite and lithium bisilicate.Glass baseplate strengthening process as described herein can be used to be strengthened for glass-ceramic substrates.
In one or more embodiments, MAS- systems glass-ceramic substrates can be in Li2SO4Strengthened in fuse salt, thus can be entered
Two Li of row+Exchange a Mg2+。
It can be about 100 microns -5 millimeters according to the thickness of the inorganic oxide substrate 110 of one or more embodiments.Show
The thickness of example inorganic oxide substrate 110 is about 100 μm-about 500 μm (such as 100,200,300,400 or 500 μm).It is other
The thickness of example inorganic oxide substrate 110 (such as 500,600,700,800,900 or 1000 μ that are about 500 μm-about 1000 μm
m).The thickness of inorganic oxide substrate 110 can be greater than about 1mm (such as about 2,3,4, or 5mm).One or more of specific
In embodiment, the thickness of inorganic oxide substrate 110 can be for 2mm or smaller or less than 1mm.Inorganic oxide substrate 110
Sour polishing can be carried out or otherwise handled, to remove or reduce the influence of surface blemish.
Optic film structure
Optic film structure as described herein has scratch resistance, and it can pass through the hardness and/or formation light of optic film structure
The hardness for learning the one or more layers of membrane structure characterizes.In one or more embodiments, such as pass through diamond shellfish
Measured by the test of Er Keweiqi pressure heads, the hardness of optic film structure is about 16GPa or bigger, about 17GPa or bigger, about 18GPa
Or bigger, about 19GPa or bigger, about 20GPa or bigger, about 22GPa or bigger.As used herein, " problem about Bellco haemodialysis ties up strange pressure head
Test " is included by following tests for measuring hardness on the surface：Tie up strange pressure head compressive surface using problem about Bellco haemodialysis has to be formed
Depth of cup apart from surface is at least about 100nm impression.Optic film structure 120 can have at least one layer, such as pass through gold
Hard rock problem about Bellco haemodialysis is tieed up measured by strange pressure head test, and at least one layer of the hardness is about 16GPa or bigger, about 17GPa or bigger,
About 18GPa or bigger, about 19GPa or bigger, about 20GPa or bigger, about 22GPa or bigger.
In one or more embodiments, optic film structure has scratch resistance, its by the reduction of scratch depth come
Measurement.Specifically, when compared with the scratch depth in the inorganic oxide substrate 110 without optic film structure, light is included
Scratch depth reduction can be presented by learning the product of membrane structure.Tie up strange pressure head using diamond problem about Bellco haemodialysis is made with the speed of 10 micro- meter per seconds
Scraper is scraped with the length of surface scraping at least 100 μm of the 160mN load along product (on the side of optic film structure)
When having the product for the optic film structure being disposed above, gained scratch depth than under same case (that is, using identical pressure
Head, load, speed and length) gained that is formed in inorganic oxide substrate 110 (without the optic film structure being arranged on)
Scratch depth is small by least about 30%, at least about 31%, at least about 32%, at least about 33%, at least about 34%, at least about 35%,
At least about 36%, at least about 37%, at least about 38%, at least about 39%, at least about 40%, at least about 41%, at least about 42%,
At least about 43%, at least about 44%, at least about 45%, at least about 46%, at least about 47%, at least about 48%, at least about 49%,
At least about 50%, at least about 51%, at least about 52%, at least about 53%, at least about 54%, at least about 55%, at least about 56%,
At least about 57%, at least about 58%, at least about 59%, at least about 60% (and all scopes between them and sub- model
Enclose).When product utilizes amorphous base material (such as glass baseplate of the glass baseplate of reinforcing and/or nonreinforcement), crystal substrate
(such as the glass-ceramic substrates of reinforcing, the glass ceramics glass baseplate of nonreinforcement, and single-crystal substrate such as sapphire) or its group
During conjunction, the property of this scratch-resistant of optic film structure may be present.In addition, when tieing up strange pressure head using diamond problem about Bellco haemodialysis, with 10
The speed of micro- meter per second scrapes at least 1mm, at least at least 2mm, 3mm to product, when at least 4mm or at least 5mm length, can deposit
In the property of this scratch-resistant of optic film structure.In one or more embodiments, optic film structure has scratch resistance,
So as to be scraped when with the strange pressure head of diamond problem about Bellco haemodialysis dimension with the speed of 10 micro- meter per seconds using 160mN load along the surface of product
When wiping at least 100 μm of length to scrape the product comprising optical film, the scratch depth that gained scrapes is less than 250nm, is less than
240nm, less than 230nm or less than 220nm.Scratch depth as described herein can be destroyed from the original of optic film structure and
Surface measure.In other words, scratch depth is not comprising any optic film structure that may be accumulated around the edge of scraping
Amount, the dislocation that optic film structure material caused by strange pressure head penetrates optic film structure is tieed up in this accumulation because of diamond problem about Bellco haemodialysis are made
Into.
In one or more embodiments, when compared with comprising sapphire naked inorganic oxide substrate 110 and with
When naked inorganic oxide substrate 110 comprising chemical enhanced glass is compared, product 100 is presented scratch depth and reduced.In one kind
Or in a variety of embodiments, relative to scraping for the product 100 of naked inorganic oxide substrate 110 comprising chemical enhanced glass
Wiping depth reduces than naked sapphire substrate relative to the naked chemical enhanced big at least twice of glass baseplate scratch depth reduction.Example
Such as, when compared with the glass baseplate of naked reinforcing, the scratch depth that 30-40% can be presented in naked sapphire substrate reduces；But when
When compared with the glass baseplate of naked reinforcing, product is presented 60-75% or bigger scratch depth and reduced.One or more specific
In embodiment, when compared with the naked inorganic oxide substrate 110 comprising chemical enhanced glass, the scraping of product 100 is deep
Degree reduction is at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75% or at least 85%, and
All scopes between them and subrange.
In one or more embodiments, optic film structure present scratch resistance, its by scrape the reduction of width come
Measurement.Specifically, when compared with the scratch depth in the inorganic oxide substrate 110 without optic film structure, light is included
Scraping width reduction can be presented by learning the product of membrane structure.Tie up strange pressure head using diamond problem about Bellco haemodialysis is made with the speed of 10 micro- meter per seconds
Scraped with the length of surface scraping at least 100 micron of the 160mN load along product (on the side of optic film structure)
During product with the optic film structure being disposed above as described herein, gained scrape width than under same case (i.e.,
Use identical pressure head, load, speed and length) in the inorganic oxide substrate 110 without the optic film structure being arranged on
The scraping width of upper formation is small by least about 30%, at least about 31%, at least about 32%, at least about 33%, at least about 34%, at least
About 35%, at least about 36%, at least about 37%, at least about 38%, at least about 39%, at least about 40%, at least about 41%, at least
About 42%, at least about 43%, at least about 44%, at least about 45% (and all scopes between them and subrange).Work as system
Product using amorphous base material (such as glass baseplate of the glass baseplate of reinforcing and/or nonreinforcement), crystal substrate (such as strengthen
Glass-ceramic substrates, the glass ceramics glass baseplate of nonreinforcement, and single-crystal substrate such as sapphire) or during its combination, can deposit
In the property of the scratch-resistant of this optic film structure.In addition, when tieing up strange pressure head using diamond problem about Bellco haemodialysis, with 10 micro- meter per seconds
Speed scrapes at least 1mm, at least at least 2mm, 3mm to product, and when at least 4mm or at least 5mm length, optical film knot may be present
The property of this scratch-resistant of structure.In one or more embodiments, optic film structure has scratch resistance, so as to golden when using
It is micro- using surface scraping at least 100 of the 160mN load along product with the speed of 10 micro- meter per seconds that hard rock problem about Bellco haemodialysis ties up strange pressure head
When the length of rice is to scrape the product comprising optical film, the scraping width that gained scrapes is less than 20nm, less than 19nm, is less than
18nm, less than 17nm, less than about 16nm, less than about 15nm, less than about 14nm, less than about 13nm, less than about 12nm, it is less than about
11nm, less than about 10nm, less than about 9nm, less than about 8nm, less than about 7nm, less than about 6nm, less than about 5nm, less than about 4nm,
Less than about 3nm, and all scopes between them and subrange.Scraping width as described herein can be from optic film structure
Original and not destroyed surface measures.In other words, scrape width and do not include what may be accumulated around the edge of scraping
The amount of any optic film structure, this accumulation tie up optical film knot caused by strange pressure head penetrates optic film structure because of diamond problem about Bellco haemodialysis
The dislocation of structure material causes.
In some embodiments, optical film prevents the formation that microcosmic ductility is scraped and/or laterally scraped.Microcosmic extension
Property scrape comprising with unrestricted length material in single groove.Microcosmic ductility scraping is laterally scraped to result in
Crackle or scraping.The length laterally scraped is similarly unrestricted, but the microcosmic extension that this is laterally scraped relative to formation
Property scrape traversed by orientation.
In one or more embodiments, it is as described herein that there is optics when being assessed using garnet paper test
Scratch resistance can be presented in the product of membrane structure.Garnet paper is tested is combined into electronic apparatus for replicating or simulating
Product routine use condition as described herein when (such as mobile phone).Using 150- granularities (grit) garnet paper (by
3M supply) manually wipe surface once after, when detecting by an unaided eye, product as described herein in its surface substantially free of
Any scraping.
In one or more embodiments, wear resistance is also presented in the product as described herein with optic film structure.
In some embodiments, wear resistance is measured by the test well known to the art, such as uses rub resistance color jail
Spend those tests of testing machine (Crockmeter), Taibo (Taber) abrasiometer and other similar reference instruments.Example
Such as, the color fastness friction resistant on the surface to be rubbed is determined using colour fastness to rubbing testing machine.Colour fastness to rubbing tries
The machine of testing causes surface directly to be contacted by the friction tips of arm of force end or " finger " with being arranged on.Colour fastness to rubbing testing machine carries
The standard finger of confession is the solid propenoic acid class bar of 15 millimeters of (mm) diameters.The standard friction cloth small pieces of cleaning are arranged on institute
State on acrylic compounds finger.Then the finger is placed on sample with 900 grams of pressure, the arm on sample mechanically
Repeatedly move back and forth, to observe the change of durability/color fastness scratch-resistant performance.The antifriction used in test as described herein
The model that color fastness testing machine is motorization is wiped, it provides 60 revs/min of uniform number of strokes.In ASTM testing procedures
The test of colour fastness to rubbing testing machine is described in F1319-94, its is entitled " for testing what is obtained by commercial replicated product
The wearability of image and standard determination method (the Standard Test Method for Determination of of pollution resistance
Abrasion and Smudge Resistance of Images Produced from Business Copy
Products) ", the full content of this article is totally incorporated herein by reference.The color fastness abrasion-resistant of the product of coating as described herein
Performance or durability are by carrying out light afterwards according to the wiping that specific times are carried out described in ASTM Test Method F1319-94
(such as reflectivity, mist degree or transparency) measurement is learned to determine.Once " wipe " and be defined as being entered with friction tips or finger
The Secondary Shocks of row two or a circulation.
As Figure 1-5, optic film structure can include one or more layers.One or more of these layers can assign light
Membrane structure and resulting product 100 are learned with the property of scratch-resistant, also provide simultaneously optics management function (such as, there is provided antireflective and/
Or water white transparency property).In one or more alternate embodiments, in optic film structure most thick layer to optic film structure and
Resulting product provides the property of scratch-resistant.The thickness of the layer of optic film structure can be changed, to adjust optic film structure and/or product
Scratch resistance.Additional or optional, one or more layers of optic film structure can include special material and/or material
Matter, so as to adjust the optical property of optic film structure and/or product.Such as layer can include transparent dielectric material such as SiO2,
GeO2,Al2O3,Nb2O5,TiO2,Y2O3With other similar materials and combinations thereof.
The thickness of optic film structure can be 1 micron or bigger.In one or more embodiments, optic film structure
Thickness can be about 2 μm or bigger.In one or more alternate embodiments, the thickness of optic film structure can be about 1 μm-about
20 μm, about 1 μm-about 15 μm, about 1 μm-about 10 μm, about 1 μm-about 8 μm, about 1 μm-about 5 μm, about 1.5 μm-about 20 μm, about 2 μm-
About 20 μm, about 2.5 μm-about 20 μm, about 3 μm-about 20 μm and all scopes between them and subrange.In some embodiment party
In formula, the thickness of optic film structure can be about 0.5 μm-about 5 μm, or about 1 μm-about 3 μm.The thickness of specific optic film structure 120
Degree can be about 1.1 μm, about 1.3 μm, about 1.4 μm, about 1.5 μm, about 1.6 μm, about 1.7 μm, about 1.8 μm, about 1.9 μm, about 2.1 μ
M, about 2.2 μm, about 2.3 μm, about 2.4 μm, about 2.5 μm, about 2.6 μm, about 2.7 μm, about 2.8 μm, about 2.9 μm, about 3.0 μm, about 4
μm, about 5 μm, about 6 μm, about 7 μm, about 8 μm, about 9 μm, about 10 μm, about 15 μm, or about 20 μm.
In visible range can be substantially limpid or transparent according to the optic film structure of one or more embodiments.
In one or more embodiments, optic film structure keeps or reduced the reflectivity of product 100, and not comprising for deliberately increasing
Any material of the big reflectivity of product 100.In one or more embodiments, the mean refractive index of optic film structure is about
1.8-2.2。
The optic film structure can include the one or more in following material：Siliceous oxide, siliceous nitride,
Siliceous nitrogen oxides, nitride (such as the AlN and Al containing aluminiumxSiyN), (such as the AlO of the nitrogen oxides containing aluminiumxNyWith
SiuAlvOxNy0) and the oxide containing aluminium, wherein x and y are more than.In one or more embodiments, SiuAlvOxNyInclude one
Kind composition, wherein (u+v)=1 and (x+y)=1.In one or more embodiments, AlOxNyInclude some compositions, wherein x+
Y=1 and x<0.5.One example of the suitably oxide containing aluminium includes Al2O3.In one or more embodiments, optics
Membrane structure includes simple layer, and the simple layer includes AlOxNy, or SiuAlvOxNy.In one or more alternate embodiments, light
AlO can be included by learning membrane structurexNyOr SiuAlvOxNy,Wherein x can be about 0- about 1.In one or more alternate embodiments, light
Learn membrane structure can also include other metal oxides, metal nitride, metal oxynitride, metal carbides, metal boride,
Diamond like carbon material and/or its combination.In addition to aluminum and silicon, illustrative metal includes B, Ti, V, Cr, Y, Zr, Nb, Mo,
Sn, Hf, Ta and W.
In one or more embodiments, optic film structure can include AlN, AlOxNy,SiAlN,SiuAlvOxNyAnd aluminium
At least one of oxide and/or Si oxide.Optionally, the optic film structure comprising AlN and aluminum oxide, which can be free of, to be contained
The nitrogen oxides of aluminium.In one or more alternate embodiments, optic film structure can include AlN and the nitrogen oxides containing aluminium.
Optionally, the optic film structure of the nitrogen oxides comprising AlN and containing aluminium can be free of the oxide containing aluminium.In embodiment
In, optic film structure can include the amount alterable of aluminum ox nitride, wherein oxygen and nitrogen, so as to exist in optic film structure containing aluminium
All three in oxide, AlN and nitrogen oxides containing aluminium.Optic film structure can include silicon, so as to which optic film structure includes
SiO2,SiOxNy,AlxSiyN,SiuAlvOxNy, and Si3N4In one or more, and oxygen, nitrogen, the amount alterable of silicon and/or aluminium
To provide any of these materials, a variety of and whole.
In one or more embodiments, material used in optic film structure can be selected to optimize optic film structure
Optical property.Such as using Al in optic film structure2O3,SiO2,SiOxNy,SiuAlvOxNyAnd AlOxNyTo cause when observation
Angle from normal incidence (that is, 0 degree) change to oblique incidence when the change of reflectivity color point reduce as far as possible.Oblique incidence
May be greater than 0 degree arrive be less than 90 degree (such as 10 degree or bigger, 20 degree or more greatly, 30 degree or more greatly, 40 degree or more greatly, 50 degree or
It is bigger, 60 degree or bigger, 70 degree or bigger, 75 degree or bigger, 80 degree or more greatly, 85 degree or more greatly, 86 degree or more greatly, 87 degree or
It is bigger, 88 degree or bigger, 89 degree or bigger or 89.5 degree or bigger).
In one or more embodiments, the amount or optical film of oxygen and/or nitrogen in optic film structure can adjust
The amount of oxygen and/or nitrogen in one or more layers of structure, so as to which refractive index of the optic film structure at about 500nm wavelength is more than
1.9.In one or more embodiments, oxygen content and/or nitrogen content are can adjust, so as to optic film structure or optical film
The refractive index that one or more layers of structure are presented at about 500nm wavelength is 1.92 or bigger, 1.94 or bigger, 1.96 or
It is bigger, 1.98 or bigger, 2.0 or bigger, 2.2 or bigger, 2.4 or bigger or 2.5 or bigger.The tool of adjustable optic film structure
Oxygen content and/or nitrogen content in body layer.Such as it can adjust in the above described manner comprising AlOxNy,SiOxNy, and/or AlxSiyN's
Oxygen content and/or nitrogen content in the layer of optic film structure.
In one or more embodiments, material used in optic film structure can be selected to optimize optic film structure
Scratch resistance.Such as Si3N4And/or AlN can account at least 50 weight % of material therefor in optic film structure 120.Si3N4With/
Or AlN optionally accounts for 55 weight % of material therefor in optic film structure 120 or more, 60 weight % or more, 65 weights
Measure % or more, 70 weight % or more or 75 weight % or more.It is additional or optional, oxygen content can be improved to adjust
Hardness, and/or dopant and alloy can be used to improve the lubricity of optic film structure 120.
Ion diffusion barrier property can be brought for the material of optic film structure by selecting.In one or more embodiments
In, optic film structure can provide diffusion barrier, and it stops that sodium ion and/or potassium ion diffuse into from inorganic oxide substrate 110
Enter other films or layer (such as optic film structure itself or any transparent electric conductive oxidation being arranged in inorganic oxide substrate
Nitride layer, antireflection layer or other this layers).
In one or more embodiments, optic film structure can include the AlN with little crystal grain polycrystalline structure.In one kind
Or in a variety of embodiments, optic film structure, which can include, has amorphous and/or microstructure AlN.Although be not intended to by
It is limited to theory, it is believed that bringing isotropism engineering properties comprising at least some impalpable structures in optic film structure, this can
Prevent to form crackle in optic film structure and/or dissipate and energy from crackle or result in the power of crackle.
In the embodiment shown in figure 2, product 200, which includes, is arranged on the opposite main of inorganic oxide substrate 110
The optic film structure 220 on one in surface 112,114.Optic film structure 220 shown in Fig. 2 includes first layer 222 and the
Two layer 224.First layer 222 includes the first sublayer 226 and the second sublayer 228, so as to which the first sublayer 226 is arranged on inorganic oxide
Between the sublayer 228 of base material 110 and second.In one or more embodiments, first layer 222 can include the oxide containing aluminium,
Nitrogen oxides, AlN or its combination, the second layer 224 containing aluminium can include transparent dielectric material such as SiO2,GeO2,Al2O3,
Nb2O5,TiO2,Y2O3With other similar materials and combinations thereof.In one or more embodiments, first layer 222 can wrap
Containing Al2O3,AlN,AlOxNy,SiAlN,SiuAlvOxNyOr its combination.In a kind of variant, the first sublayer 226 can include Al2O3。
In another variant, the first sublayer can include AlOxNy.Again in another variant, the second sublayer 228 includes AlN.In one kind
In embodiment, optic film structure 220 includes first layer 222 and the second layer 224, and the first layer 222 includes including Al2O3
One sublayer 226 and the second sublayer 228 comprising AlN, the second layer 224 include transparent dielectric material (such as SiO2,GeO2,
Al2O3,Nb2O5,TiO2,Y2O3With other similar materials and combinations thereof).In another embodiment, optic film structure 220 wraps
Containing first layer 222 and the second layer 224, the first layer 222 includes including AlOxNyThe first sublayer 226 and comprising AlN second son
Layer 228, the second layer 224 include transparent dielectric material (such as SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With other classes
Like material and combinations thereof).Al is being utilized wherein in the second layer 2242O3Embodiment in, nitrogen and oxygen concentration can be changed
To form Al2O3,AlOxNyAnd/or AlN, to form the layer of optic film structure.
In one or more embodiments, the second sublayer 228 can include AlN, AlOxNy,SiAlN,SiuAlvOxNy
Or its combination, and it is thicker than the first sublayer 226 and/or the second layer 224 or much thick.In one or more embodiments,
The thickness of two sublayers 228 is more than or noticeably greater than the first sublayer 226 and the thickness sum of the second layer 224.In a kind of variant, the
The thickness of two sublayers 228 can be 1 μm or bigger.Such as second the thickness of sublayer 228 can be about 1 μm-about 3 μm or specifically
About 2 μm-about 3 μm.Embodiment can include the second sublayer 228, and its thickness is about 1.1 μm or bigger, about 1.2 μm or more
Greatly, about 1.3 μm or bigger, about 1.4 μm or bigger, about 1.5 μm or bigger, about 1.6 μm or bigger, about 1.7 μm or bigger, about
1.8 μm or bigger, about 1.9 μm or bigger, about 2 μm or bigger, about 2.1 μm or bigger, about 2.2 μm or bigger, about 2.3 μm or more
Greatly, about 2.4 μm or bigger, about 2.5 μm or bigger, about 2.6 μm or bigger, about 2.7 μm or bigger, about 2.8 μm or bigger, about
2.9 μm or bigger, or about 3 μm or bigger.In the embodiment that wherein the second sublayer 228 includes AlN, the thickness of the second sublayer
It can be about 2 μm or bigger.Such as second sublayer thickness can be about 2.2 μm or bigger, about 2.3 μm or bigger, about 2.4 μm or
It is bigger, about 2.5 μm or bigger, about 2.6 μm or bigger, about 2.7 μm or bigger, about 2.8 μm or bigger, about 2.9 μm or bigger, or
About 3 μm or bigger.The first sublayer 226 and the exemplary thickness of the second layer 224 are enumerated in embodiment herein, it can be changed
To provide optical property as described herein.
In some embodiments, the second thicker sublayer 228 of use is (such as with greater than about 5 μm, or greater than about 10 μ
M thickness) optical property strengthened is provided.For example, in some cases, reduced or eliminated using thicker sublayer 228 with angle
Spend the metamerism (angular metamerism) of different generations.When viewing angle is oblique incidence, sent out with angle is different
Raw metamerism causes the transparency of observation or reflectivity that color change occurs.In some designs of optical film, reflected light
Spectrum or transmitted spectrum include vibration on visible spectrum.In some cases, when viewing angle changes to inclination from normal incidence
When incident, these vibrations move.When the line width of light source is narrower the line width of spectrum component (such as in F02 light sources), in vibration
This movement (and therefore exist more easily by color change to observe (in a manner of transparency or reflectivity change) with angle
Spend the metamerism of different generations).When the line width of light source is wider the line width of spectrum component (such as in D65 light sources), in vibration
This movement less easily or can not color change come observe (by transparency or reflectivity change in a manner of) (and because
This is reduced or eliminated with the different metamerisms occurred of angle).Although being not intended to be limited to theory, it is believed that using thicker second
Sublayer at least reduces or can even eliminated the metamerism with the different generations of angle under whole or special light sources.This light source
The standard sources determined comprising such as CIE, such as A light sources (representing that tungsten filament lights), B light sources (daylight analog light source), illuminant-C
(daylight analog light source), D series of light sources (expression natural daylight), and F series of light sources (representing various types of fluorescence radiations).
In embodiment, using the second thicker sublayer can reduce or eliminate under F02 light sources with angle it is different occur it is same
The different spectrum of color.When viewing angle be oblique incidence and with normal incidence into about 0 Du-about 80 degree, about 0 Du-about 75 degree, about 0 Du-about 70
Degree, about 0 Du-about 65 degree, about 0 Du-about 60 degree, about 0 Du-about 55 degree, about 0 Du-about 50 degree, about 0 Du-about 45 degree, about 0 Du-about
40 degree, about 0 Du-about 35 degree, about 0 Du-about 30 degree, about 0 Du-about 25 degree, about 0 Du-about 20 degree, about 0 Du-about 15 degree, about 5 degree-
About 80 degree, about 5 Dus-about 80 degree, about 5 Dus-about 70 degree, about 5 Dus-about 65 degree, about 5 Dus-about 60 degree, about 5 Dus-about 55 degree, about 5
Du-about 50 degree, about 5 Dus-about 45 degree, about 5 Dus-about 40 degree, about 5 Dus-about 35 degree, about 5 Dus-about 30 degree, about 5 Dus-about 25 degree, about
5 Dus-about 20 degree, about 5 Dus-about 15 degree, and when all scopes between them and subrange, by using thicker second
Sublayer can be reduced or even eliminated with the different metamerisms occurred of angle.For with normal incidence into about 0 Du-about 80 degree of institute
For having oblique incidence angle, the metamerism with the different generations of angle of reduction can be presented in optical film.
The refractive index of first sublayer 226 can be about 1.45- about 1.8.In one or more embodiments, the first son
The refractive index of layer 226 can be about 1.6- about 1.75.Such as first the refractive index of sublayer 226 can include 1.45,1.46,1.47,
1.48,1.49,1.5,1.51,1.52,1.53,1.54,1.55,1.56,1.57,1.58,1.59,1.60,1.61,1.62,
1.63,1.64,1.65,1.66,1.67,1.68,1.69,1.70,1.71,1.72,1.73,1.74,1.76,1.77,1.78,
1.79,1.8 all scopes and between them and subrange, it may be present in multiple positions along the first sublayer.The
The refractive index of two sublayers 228 can be about 1.8- about 2.2.In one or more embodiments, the refractive index of the second sublayer can be
About 2.0- about 2.15.Such as second the refractive index of sublayer 228 can include 1.8,1.82,1.84,1.86,1.88,1.90,1.92,
1.94,1.96,1.98,1.99,2.0,2.02,2.04,2.06,2.08,2.1,2.12,2.14,2.15,2.16,2.18,2.2
And all scopes between them and subrange, it may be present in multiple positions along the second sublayer.The second layer 224
Refractive index can be about 1.4- about 1.6.In a specific embodiment, the refractive index of the second layer 224 can be about 1.45- about 1.55.Example
Such as, the refractive index of the second layer 224 can include 1.4,1.42,1.44,1.46,1.48,1.50,1.52,1.54,1.56,1.58,
1.6 and all scopes between them and subrange, it may be present in multiple positions along the second layer.
Fig. 7 totally shows the optical property of the optic film structure 220 shown in Fig. 2.In the picture, the thickness number in x-axis
Value is represented in the thickness away from the optic film structure 220 on the direction of inorganic oxide substrate 110.Optical film knot is provided on the y axis
The refractive index value of structure 220, to show the variations in refractive index along the thickness of optic film structure.Fig. 7 picture does not account for nothing
Machine oxide base material 110 (or any other layer between inorganic oxide substrate 110 and optic film structure 220) or air
The refractive index of (being arranged on any other layer on optic film structure 220).The sublayer 226 of inorganic oxide substrate 110 and first it
Between interface represent that the interface between the first sublayer 226 and the second sublayer 228 is by the table of reference 610 by reference 600
Showing, the interface between the second sublayer 228 and the second layer 224 is represented by reference 620, and between the second layer 224 and air
Interface is represented by reference 630.As shown in Figure 7, the first sublayer 226 and the refractive index of the second layer 224 are less than the second sublayer 228
Refractive index.In a specific embodiment, the refractive index of the first sublayer 226 is about 1.75, and the refractive index of the second sublayer is about
2.1, the refractive index of the second layer 224 is about 1.5.In the figure 7, the thickness of the second sublayer 228 is more than the first sublayer 226 and the second layer
224 thickness.
In the embodiment shown in Fig. 3, product 300, which includes, is arranged on the opposite main of inorganic oxide substrate 110
The optic film structure 320 on one in surface 112,114.Optic film structure 320 shown in Fig. 3 includes first layer 322 and the
Two layer 324.First layer 322 includes the first sublayer 326, the second sublayer 328 and the 3rd sublayer 330.In the embodiment shown in Fig. 3
In, in first layer 320, the second sublayer 328 is between the first sublayer 326 and the 3rd sublayer 330.First sublayer 326 is arranged on
Between the sublayer 328 of inorganic oxide substrate 110 and second, while the 3rd sublayer 330 is arranged on the second sublayer 328 and the second layer
Between 324.In one or more embodiments, first layer 322 can include the oxide containing aluminium, the nitrogen oxides containing aluminium, AlN
Or its combination, and transparent dielectric material can be also included (for example, SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With it is other similar
Material and combinations thereof).In one or more embodiments, first layer 322 can include Al2O3,AlN,AlOxNyOr its group
Close, and can also include transparent dielectric material (such as SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With other similar materials and
It is combined).The second layer 324 can include transparent dielectric material (such as SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With it is other
Similar material and combinations thereof).In a kind of variant, the first sublayer 326 can include AlN, and the second sublayer 328 can include SiO2, the
Three sublayers 330 can include AlN.In another variant, the first sublayer 326 can include AlN, and the second sublayer 328 can include Al2O3,
3rd sublayer 330 can include AlN.Al is wherein being utilized in the second sublayer 328 and the second layer 3242O3Embodiment in, can
Change nitrogen and oxygen concentration to form Al2O3Or AlN, so as to form the layer of optic film structure.
In one or more embodiments, the first sublayer 326 and 330 respective thickness of the 3rd sublayer or they
Thickness sum can be more than or the noticeably greater than thickness of the second sublayer 328 or the second layer 324.In one or more embodiments,
First sublayer 326 and 330 respective thickness of the 3rd sublayer or their thickness sum can be more than or noticeably greater than the second sublayer 328
With the thickness sum of the second layer 324.In a kind of variant, the first sublayer 326 and/or 330 respective thickness of the 3rd sublayer or it
Thickness sum can be about 1 μm or bigger.Such as first sublayer 326 and/or 330 respective thickness of the 3rd sublayer or they
Thickness sum can be about 1.1 μm or bigger, about 1.2 μm or bigger, about 1.3 μm or bigger, about 1.4 μm or bigger, about 1.5 μm
Or it is bigger, about 1.6 μm or bigger, about 1.7 μm or bigger, about 1.8 μm or bigger, about 1.9 μm or bigger, or about 2 μm or bigger.
In wherein the first sublayer 326 and/or the 3rd sublayer 330 include AlN embodiment, these 326,328 respective thickness of sublayer
Degree or their thickness sum can be about 2 μm or bigger.Such as first sublayer 326 and/or 328 respective thickness of the 3rd sublayer
Or their thickness sum can be about 2.1 μm or bigger, about 2.2 μm or bigger, about 2.3 μm or bigger, about 2.4 μm or bigger,
About 2.5 μm or bigger, about 2.6 μm or bigger, about 2.7 μm or bigger, about 2.8 μm or bigger, about 2.9 μm or bigger, or about 3 μm
It is or bigger.In one or more embodiments, the first sublayer 326 can have the thickness identical or different with the 3rd sublayer 330.
The thickness of first sublayer 326 can be more than or less than the thickness of the 3rd sublayer 330.In one or more embodiments, the second son
Layer 328 is identical with the thickness of the second layer 324.In one or more alternate embodiments, optic film structure 320 have it is thick/thin/
Thick/thin thickness form, wherein first and the 3rd sublayer 326,330 be thicker, and second-sublayer 328 and the second layer 324 are relative
In first and the 3rd sublayer 326,330 be relatively thin.
The refractive index of first sublayer 326 can be about 1.7- about 2.1.Such as first the refractive index of sublayer 326 can include
1.70,1.72,1.74,1.76,1.78,1.80,1.82,1.84,1.86,1.88,1.90,1.92,1.94,1.96,1.98,
2.0,2.1 all scopes and between them and subrange.In one or more alternate embodiments, refractive index and the
The hardness increase of one sublayer 326 is related.The refractive index of 3rd sublayer 330 can be about 1.7- about 2.1.In one or more embodiment party
In formula, the refractive index of the 3rd sublayer 330 can be about 2.0- about 2.1.Such as the 3rd sublayer 330 refractive index can include 1.70,
1.72,1.74,1.76,1.78,1.80,1.82,1.84,1.86,1.88,1.90,1.92,1.94,1.96,1.98,2.0,2.1
And all scopes between them and subrange.In one or more alternate embodiments, refractive index and the first sublayer
326 hardness increase is related.The refractive index of second sublayer 328 can be about 1.45- about 1.8.In one or more embodiments,
The refractive index of second sublayer 328 can be about 1.65- about 1.75.Such as second the refractive index of sublayer 328 can be 1.45,1.46,
1.48,1.50,1.52,1.54,1.56,1.58,1.60,1.62,1.64,1.65,1.66,1.67,1.68,1.69,1.70,
1.71,1.72,1.73,1.74,1.75,1.76,1.78,1.8 and all scopes between them and subrange.The second layer
324 refractive index can be about 1.45- about 1.8.In one or more embodiments, the refractive index of the second sublayer 328 can be about
1.45- about 1.55.Such as second the refractive index of sublayer 328 can be 1.45,1.46,1.47,1.48,1.49,1.50,1.51,
1.52,1.53,1.54,1.55,1.56,1.58,1.60,1.62,1.64,1.65,1.66,1.67,1.68,1.69,1.70,
1.71,1.72,1.73,1.74,1.75,1.76,1.78,1.8 and all scopes between them and subrange.
Fig. 8 totally shows the optical property of the optic film structure 320 shown in Fig. 3.In the picture, the thickness number in x-axis
Value is represented in the thickness away from the optic film structure 320 on the direction of inorganic oxide substrate 110.Optical film knot is provided on the y axis
The refractive index value of structure 320, to show the variations in refractive index along the thickness of optic film structure.Fig. 8 picture does not account for nothing
Machine oxide base material 110 (or any other layer between inorganic oxide substrate 110 and optic film structure 320) or air
The refractive index of (being arranged on any other layer on optic film structure 320).The sublayer 326 of inorganic oxide substrate 110 and first it
Between interface represent that the interface between the first sublayer 326 and the second sublayer 328 is by the table of reference 710 by reference 700
Show, the interface between the second sublayer 328 and the 3rd sublayer 330 is represented by reference 720, the 3rd sublayer 330 and the second layer 324
Between interface represent that and the interface between the second layer 324 and air is represented by reference 740 by reference 730.Such as figure
Shown in 8, the refractive index of the first sublayer 326 and the 3rd sublayer 330 is more than the refractive index of the second sublayer 328 and the folding of the second layer 324
Penetrate rate.In the embodiment shown in Fig. 8, the refractive index of the first sublayer 326 and the 3rd sublayer 330 is shown as being equal to each other, and
Second sublayer 328 and the refractive index of the second layer 324 are shown as being equal to each other.In one or more alternate embodiments, first
The refractive index of sublayer 326 may differ from the refractive index of the 3rd sublayer 330, and the refractive index of the second sublayer 328 may differ from the second layer
324 refractive index.In fig. 8, first and the 3rd the thickness of sublayer 326,330 be shown as being more than the second sublayer 328 and the second layer
324 thickness.In addition, the thickness of the 3rd sublayer 330 is shown as the thickness more than the first sublayer 324；But the first sublayer 324
Thickness can be more than the 3rd sublayer 330 thickness.
In the embodiment shown in Fig. 4, product 400, which includes, is arranged on the opposite main of inorganic oxide substrate 110
The optic film structure 420 on one in surface 112,114.Optic film structure 420 shown in Fig. 4 includes first layer 422 and the
Two layer 424.First layer 422 includes siliceous oxide, siliceous nitrogen oxides, silicon nitride, the oxide containing aluminium, the nitrogen containing aluminium
Oxide (such as AlOxNyAnd SiuAlvOxNy), nitride containing aluminium (such as AlN and AlxSiyN) or it is combined.The second layer
424 can include transparent dielectric material (such as SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With other similar materials and its group
Close).
First layer 422 can include oxygen content gradient, nitrogen content gradient, silicone content gradient and aluminium content gradient and they
At least one of various combination.As used herein, term " gradient " refers to the atom % changes of the element in the composition of layer.Can
Occur the atom % changes of element in multiple sublayers of layer.In some cases, it is available that there is different elements each other
For up to the 10,20,30,40,50,60,70,80,90,100,110,120 or even 130 sublayers have to be formed of atom %
The layer of gradient.In the layer comprising oxygen gradient, the group at or near interface between this layer and inorganic oxide substrate 110
The amount of oxygen (atom %) in, may differ from interface between the layer and another layer (for example, first layer and second layer) it
At or near and other regions between them composition in oxygen (atom %) amount.
In one or more embodiments, composition gradient can include the atom % of silicon/aluminium composition gradient, wherein silicon and aluminium
Changed independently of one another or related to each other along the thickness of first layer.In other embodiments, composition gradient can wrap
Thickness of the atom % of oxygen-containing/nitrogen composition gradient, wherein oxygen and nitrogen along first layer occurs independently of one another or related to each other
Change.In one or more embodiments, at or near the interface between inorganic oxide substrate 110 and first layer 422
Oxygen and the ratio of nitrogen can be more than the ratio of oxygen and nitrogen at or near interface between first layer 422 and the second layer 424.Example
Such as, may be present very at or near the interface in first layer 422 between inorganic oxide substrate 110 and first layer 422
At or near few nitrogen or in the absence of nitrogen, and/or interface in first layer 422 between first layer 422 and the second layer 424
Considerably less oxygen may be present or in the absence of oxygen.In one or more embodiments, inorganic oxide substrate 110 and first layer
The ratio of silicon at or near interface and aluminium between 422 can be more than in place of the interface between first layer 422 and the second layer 424
Or neighbouring silicon and the ratio of aluminium.Such as the boundary in first layer 422 between inorganic oxide substrate 110 and first layer 422
Considerably less aluminium may be present at or near face or in the absence of aluminium, and/or in first layer 422 and the second layer in first layer 422
Considerably less silicon may be present at or near interface between 424 or in the absence of silicon.
In one or more embodiments, oxygen content gradient and/or nitrogen content gradient can be by introducing in deposition process
The oxygen of (that is, into the deposition chambers for wherein depositing to optic film structure in inorganic oxide substrate) and/or nitrogen
Flow controls.In order to increase oxygen or nitrogen content, increase the flow of oxygen or nitrogen.In some embodiments, can be drawn by control
Lead on aluminium and/or silicon source material power (such as when using sputtering to form optic film structure when, control be directed to aluminium and/
Or the power on silicon sputtering target) control aluminium and/or silicon gradient.In order to increase aluminium or silicone content, increase guiding to aluminium and/or silicon
The power of source material.
Oxygen and/or silicone content in first layer 422 can along first layer 422 thickness t, surpass away from inorganic oxide base
The direction of material 110 reduces, as shown in Figure 6A.Oxygen content and/or silicone content gradient can prolong along the integral thickness t of first layer 422
Stretch.In another variant, oxygen content and/or silicone content gradient can extend along the thickness t of first layer 422 part, and
The remainder of first layer 422 can not include oxygen content and/or silicone content gradient, and thus can have constant oxygen and/or silicon
Content (it can be free of oxygen and/or silicon).For example, following article institute is described in more detail, oxygen content and/or silicone content gradient are sustainable
Until the interface between optic film structure and inorganic oxide substrate 110 or in inorganic oxide substrate 110 and include oxygen content
And/or any other layer (such as intermediate layer) between the layer of silicone content gradient.Or oxygen content and/or silicone content gradient can
Stop at a certain distance from inorganic oxide substrate 110, or be arranged on inorganic oxide substrate 110 and first layer 422
Between intermediate layer at stop.In one or more embodiments, the oxygen content of first layer 422 and/or silicone content can be in light
It is maximum to learn the near interface between membrane structure 420 and inorganic oxide substrate 110, and first layer 422 and the second layer 424 it
Between near interface for minimum.In one or more embodiments, the composition of first layer 422 may depend on first layer 422
Oxygen content and/or silicone content.Such as first layer 422 can be in the region of the first layer 422 of neighbouring inorganic oxide substrate 110
The oxygen content and/or silicone content contained up to.First layer 422 can include in the region of the first layer 422 of the neighbouring second layer 424
Minimum oxygen content and/or silicone content, such as embodiment as shown in Figure 5.
In one or more embodiments, the region Ke Bao of the first layer 422 of neighbouring inorganic oxide substrate 110
Oxygen content containing highest and nitrogen content (i.e. y=0) is not included.In a kind of this embodiment, neighbouring inorganic oxide
The region of the first layer 422 of base material 110 can include Al2O3、SiO2Or its combination.
In one or more embodiments, first layer 422 can include aluminium content gradient and/or nitrogen content gradient.First
Layer 422 in aluminium content and/or nitrogen content can along the thickness t of first layer 422, towards thickness t away from inorganic oxide substrate
110 direction increase, as shown in Figure 6B.Aluminium content and/or nitrogen content gradient can extend along the integral thickness t of first layer 422.
In another variant, aluminium content and/or nitrogen content gradient can extend along the thickness t of first layer 422 part, and first
The remainder of layer 422 can not include aluminium content and/or nitrogen content gradient, and thus can have constant aluminium and/or nitrogen content
(it can be free of aluminium and/or nitrogen).For example, following article institute it is described in more detail, aluminium content and/or nitrogen content gradient it is sustainable until
Interface between optic film structure and inorganic oxide substrate 110 or inorganic oxide substrate 110 and comprising aluminium content and/or
Any other layer (such as intermediate layer) between the layer of nitrogen content gradient.Or aluminium content and/or nitrogen content gradient can be in distances
Stop at a certain distance from inorganic oxide substrate 110, or be arranged between inorganic oxide substrate 110 and first layer 422
Stop at intermediate layer.In one or more embodiments, the aluminium content of first layer 422 and/or nitrogen content can be in optical film knots
Near interface between structure 420 and inorganic oxide substrate 110 is minimum, and the boundary between first layer 422 and the second layer 424
Face is nearby maximum.Fig. 6 B show the relative aluminium content and/or nitrogen content of first layer 424.In one or more embodiments,
Depending on the silicone content of first layer 422, oxygen content, aluminium content and/or nitrogen content, first layer 422 includes Si oxide, silicon nitrogen oxygen
Compound, silicon nitride, the oxide containing aluminium, nitrogen oxides (such as the AlO containing aluminiumxNyAnd SiuAlvOxNy) or nitride containing aluminium
(such as AlN and AlxSiyN).Such as first layer 422 can be in the region of the first layer 422 of the neighbouring second layer 424 comprising minimum
Silicone content and/or oxygen content, as shown in Figure 6A.Also as shown in Figure 6A, first layer 422 can be in neighbouring inorganic oxide substrate 110
First layer 422 region in the oxygen content that contains up to and/or silicone content.Fig. 4 A show a kind of embodiment, wherein first
Layer 422 includes silicon gradient, aluminium gradient, oxygen gradient and nitrogen gradient.In Figure 4 A, silicon and oxygen content are along away from inorganic oxide base
The thickness direction of material 110 reduces, and aluminium and nitrogen content increase along the thickness direction away from inorganic oxide substrate 110.Although figure
The relative quantity of each in 4A displays silicon, aluminium, oxygen and nitrogen；But, it should be noted that silicon, aluminium, the changes of contents of oxygen and nitrogen can not be
It is linear or consistent, and can have SiO at the different-thickness of first layer 4222,SiOxNy,SiuAlvOxNy,AlxSiyN and
AlN mixture.
Between the region of neighbouring inorganic oxide substrate 110 and the region of the neighbouring second layer 424, first layer 422 can wrap
Containing AlOxNy, wherein x and y depend on the amount of existing nitrogen, and can be as nitrogen content is along away from inorganic oxide substrate 110
Direction increases and changed along thickness t.In addition, in the region of neighbouring inorganic oxide substrate 110 and the area of the neighbouring second layer 424
Between domain, first layer 422 can include SiuAlvOxNy(wherein (u+v)=1 and (x+y)=1) or SiOxNyWherein x and y are depended on
The amount of existing nitrogen and/or aluminium, and can be as nitrogen content and/or aluminium content are away from the direction edge of inorganic oxide substrate 110
Thickness t increases and change.
In another embodiment, first layer includes SiuAlvOxNyAnd/or SiOxNy, wherein along the of thickness t
In one layer 422 of at least one region, x or y can be equal to zero.In one or more embodiments, neighbouring inorganic oxide
The region of the first layer 422 of thing base material 110 can not include nitrogen content and the oxygen content (i.e. y=0) contained up to.In one kind so
Embodiment in, the region of the first layer 422 of neighbouring inorganic oxide substrate 110 can include SiO2.Have in another kind
In body embodiment, the nitrogen content and/or highest aluminium that can be contained up to adjacent to the region of the first layer 422 of the second layer 424 contain
Amount and minimum oxygen content and/or minimum silicone content.In this embodiment, the first layer 422 of the neighbouring second layer 424
Region can include AlN, Si3N4Or AlxSiyN。
In one or more embodiments, the first layer 422 of neighbouring inorganic oxide substrate 110 includes SiO2Or it is rich in
Silicon and/or oxygen and it can lack or lack aluminium and/or nitrogen.In one or more embodiments, the first layer of the neighbouring second layer 424
422 comprising AlN or rich in aluminium and/or nitrogen and can lack or lack silicon and/or oxygen.
In another embodiment, first layer includes AlOxNy, wherein at least one of the first layer 422 along thickness t
In individual region, y can be equal to zero.In one or more embodiments, the first layer of neighbouring inorganic oxide substrate 110
Oxygen content that 422 region can contain up to and nitrogen content (i.e. y=0) is not included.In a kind of such embodiment,
The region of the first layer 422 of neighbouring inorganic oxide substrate 110 can include Al2O3。
In one or more embodiments, the composition of adjustable ganglionic layer 422, so as to which viewing angle will be worked as from normal incidence
The change of reflectivity color point when (that is, 0 degree) changes to oblique incidence reduces as far as possible.In this embodiment, layer 422
Composition be gradient distribution, so as near interface between first layer 422 and the second layer 424, first layer includes AlN,
AlxSiyN,Si3N4,SiuAlvOxNy(wherein x<Or AlO 0.1)xNy(wherein x<0.1).
In one or more embodiments, the thickness of first layer 422 is more than or the noticeably greater than second layer 424.
In a kind of variant, the thickness of first layer 422 can be 1 μm or bigger.Such as the thickness of first layer 422 can be for 1.1 μm or bigger,
1.2 μm or bigger, 1.3 μm or bigger, 1.4 μm or bigger, 1.5 μm or bigger, 1.6 μm or bigger, 1.7 μm or bigger, 1.8 μm
Or it is bigger, 1.9 μm or bigger, 2 μm or bigger, 2.1 μm or bigger, 2.2 μm or bigger, 2.3 μm or bigger, 2.4 μm or bigger,
2.5 μm or bigger, 2.6 μm or bigger, 2.7 μm or bigger, 2.8 μm or bigger, 2.9 μm or bigger, or 3 μm or bigger.
In the embodiment shown in Fig. 4, the refractive index of first layer 422 can be about 1.6- about 2.1.Such as first layer 422
Refractive index can include 1.6,1.62,1.64,1.66,1.68,1.70,1.72,1.74,1.76,1.78,1.80,1. 82,
1.84,1.86,1.88,1.90,1.92,1.94,1.96,1.98,2.0,2.1 all scopes and between them and sub- model
Enclose.The refractive index of the second layer 424 can be about 1.45- about 1.55.Such as the refractive index of the second layer 424 can include 1.45,1.46,
1.47,1.48,1.49,1.50,1.51,1.52,1.53,1.54,1.55 and all scopes between them and subrange.
Following article institute is described in more detail, and the first layer 422 of optic film structure 420 can have refractive index gradient.
Al is being utilized wherein in the second layer 4242O3A kind of embodiment in, nitrogen can be changed and oxygen concentration carrys out shape
Into Al2O3,AlOxNyAnd/or any of AlN, to form the layer of optic film structure.
In one or more alternate embodiments, optic film structure 420 can not include the second layer 424 and can only include the
One layer 422.
Fig. 9 totally shows the optical property of the optic film structure 420 shown in Fig. 4.In the picture, the thickness number in x-axis
Value is represented in the thickness away from the optic film structure 420 on the direction of inorganic oxide substrate 110.Optical film knot is provided on the y axis
The refractive index value of structure 420, to show the variations in refractive index along the thickness of optic film structure.Fig. 9 picture does not account for nothing
Machine oxide base material 110 (or any other layer between inorganic oxide substrate 110 and optic film structure 420) or air
The refractive index of (or any other layer being arranged on optic film structure 420).Inorganic oxide substrate 110 and first layer 422 it
Between interface represent that the interface between first layer 422 and the second layer 424 is represented by reference 810 by reference 800,
Two layers of interface between 424 and air is represented by reference 820.As shown in Figure 9, the refractive index of first layer 422 is along remote
The direction of inorganic oxide substrate 110 (or bed boundary of inorganic oxide substrate-the first 800) increases along thickness.A kind of or
In numerous embodiments, refractive index changes with the change of the oxygen content in first layer 422.In fig.9, for first layer
For 422 more parts, the refractive index of first layer 422 is more than the refractive index of the second layer 424.In other words, first layer 422
The refractive index of major part is higher than the refractive index of the second layer 424.In fig.9, the thickness of first layer 422 is shown as being more than the second layer
424 thickness.
Fig. 5 shows product 500, and it includes and is arranged in the opposite major surfaces 112,114 of inorganic oxide substrate 110
One on optic film structure 520.Optic film structure 520 shown in Fig. 5 includes first layer 522 and the second layer 524.First layer
522 comprising siliceous oxide, siliceous nitrogen oxides, silicon nitride, the oxide containing aluminium, containing aluminium nitrogen oxides (such as
AlOxNyAnd SiuAlvOxNy), nitride containing aluminium (such as AlN and AlxSiyN) or it is combined.The second layer 524 can include transparent
Dielectric material (such as SiO2,GeO2,Al2O3,Nb2O5,TiO2,Y2O3With other similar materials and combinations thereof) or its combination.
First layer 522 includes the first sublayer 526 and the second sublayer 528.As described in reference optical membrane structure 420, the first sublayer 526 can wrap
Oxygen-containing concentration gradients, nitrogen content gradient, silicone content gradient and aluminium content gradient and its various combination.
In one or more embodiments, oxygen content, silicone content, nitrogen content and/or the aluminium depending on the first sublayer 526
Content, the first sublayer 526 include siliceous oxide, siliceous nitrogen oxides, silicon nitride, the oxide containing aluminium, the nitrogen containing aluminium
Oxide (such as AlOxNyAnd SiuAlvOxNy), nitride containing aluminium (such as AlN and AlxSiy), and/or combinations thereof N.
In a specific embodiment, the first sublayer 526 can be free of AlN and/or Si3N4.In other words, one or more specific embodiment parties
The full depth t of the first sublayer 526 of formula includes oxygen, but the amount of oxygen changes along thickness t.Second sublayer 528 can include AlN and/
Or Si3N4.In one or more embodiments, the second sublayer 528 can be free of any oxygen deliberately included.Therefore, a kind of or
In numerous embodiments, the oxygen content gradient of first layer 522 can extend only along the thickness t of the first sublayer 526, and the second sublayer
528 can be free of oxygen.
Fig. 5 A show a kind of embodiment, wherein the first sublayer 526 includes silicon gradient, aluminium gradient, oxygen gradient and nitrogen gradient.
In fig. 5, silicon and oxygen content reduce along the thickness direction away from inorganic oxide substrate 110, and aluminium and nitrogen content are along remote
The thickness direction increase of inorganic oxide substrate 110.Although the relative quantity of each in display silicon, aluminium, oxygen and nitrogen；But should
Point out silicon, aluminium, oxygen and nitrogen changes of contents can not be it is linear or consistent, and can be in the different-thickness of the first sublayer 526
SiO be present in place2,SiOxNy,SiuAlvOxNy,AlxSiyN and AlN mixture.In one or more embodiments, the first son
Layer can not include AlN and only can include SiO2,SiOxNy,SiuAlvOxNy, and/or AlxSiyN, the second sublayer can include
AlN。
In one or more embodiments, oxygen, silicon, aluminium and/or nitrogen content are along away from inorganic oxide substrate 110
Thickness t of the direction along the sublayer 526 of first layer 422 or first reduction or increase can be constant.Substituted in one or more
In embodiment, oxygen, silicon, the reduction of aluminium and/or nitrogen or increase are not constant.The reduction of oxygen, silicon, aluminium and/or nitrogen wherein
Or increase is not in constant this embodiment, it should be appreciated that oxygen, silicon, aluminium and/or nitrogen are along away from inorganic oxide substrate 110
Part of the direction along thickness t will reduce or keep constant；But as total trend, the sublayer 526 of first layer 422 or first
Each oxygen, silicon, aluminium and/or nitrogen content will along away from inorganic oxide substrate 110 direction along thickness t reduce or increase.
Such as the layer of the optic film structure as described herein with oxygen content gradient does not include oxygen content along away from inorganic oxide base
Increase of the direction of material 110 along thickness t.Wherein thickness t of the oxygen content along the sublayer 526 of first layer 422 or first part
Reduce or keep the oxygen content gradient of constant embodiment, " progressively form " oxygen content gradient can be referred to as or can be described as having
There is the oxygen content that the thickness along the sublayer 526 of first layer 422 or first reduces step by step.In one or more embodiments
In, along the thickness of the sublayer 526 of first layer 422 or first closer to inorganic oxide substrate 110, oxygen content can be slower
Rate reduction, and along the thickness of the sublayer 526 of first layer 422 or first closer to the sublayer 528 of the second layer 424 or second, oxygen
Content can faster rate reduction.In other words, reduced along the oxygen content of the thickness of the sublayer 526 of first layer 422 or first
Speed can increase along the direction away from inorganic oxide substrate 110.Therefore, oxygen content gradient can be along away from inorganic oxide
The direction of base material linearly or non-linearly increases along thickness t.These types gradient (it is i.e., step by step, constant, faster/
It is slower speed, linear and nonlinear) silicone content gradient, aluminium gradient and nitrogen gradient as described herein are equally applicable to,
The wherein thickness increase and reduction of silicone content, aluminium content and/or nitrogen content along the sublayer 526 of first layer 422 or first.
In one or more embodiments, the thickness that can adjust second sublayer 528 optimizes the hardness of optic film structure.
In one or more embodiments, the thickness of the second sublayer 528 can be adjusted relative to the first sublayer 526.In one kind
Or in a variety of embodiments, the sublayer 526 of the second sublayer 528 to the first or the second layer 524 are thicker or significantly thicker.In one kind
Or in numerous embodiments, the thickness of the second sublayer 528 is more than or the noticeably greater than thickness of the first sublayer 526 and the second layer 524
Sum.In a kind of variant, the thickness of the second sublayer 528 can be 1 μm or bigger.Such as second the thickness of sublayer 528 can be about
1 μm-about 3 μm or specifically about 2 μm-about 3 μm.The thickness of the embodiment of second sublayer 528 can be about 1.1 μm or more
Greatly, about 1.2 μm or bigger, about 1.3 μm or bigger, about 1.4 μm or bigger, about 1.5 μm or bigger, about 1.6 μm or bigger, about
1.7 μm or bigger, about 1.8 μm or bigger, about 1.9 μm or bigger, about 2 μm or bigger, about 2.1 μm or bigger, about 2.2 μm or more
Greatly, about 2.3 μm or bigger, about 2.4 μm or bigger, about 2.5 μm or bigger, about 2.6 μm or bigger, about 2.7 μm or bigger, about
2.8 μm or bigger, about 2.9 μm or bigger, or about 3 μm or bigger.In the embodiment that wherein the second sublayer 528 includes AlN,
The thickness of second sublayer can be 2 μm or bigger.Such as second sublayer 528 thickness can be about 2.2 μm or bigger, about 2.3 μm or
It is bigger, about 2.4 μm or bigger, about 2.5 μm or bigger, about 2.6 μm or bigger, about 2.7 μm or bigger, about 2.8 μm or bigger, about
2.9 μm or bigger, or about 3 μm or bigger.
The refractive index of first sublayer 526 can be about 1.6- about 2.1.Such as first sublayer 326 refractive index can include 1.6,
1.62,1.64,1.66,1.68,1.70,1.72,1.74,1.76,1.78,1.80,1.82,1.84,1.86,1.88,1.90,
1.92,1.94,1.96,1.98,2.0,2.1 and all scopes between them and subrange.The refraction of second sublayer 528
Rate can be about 2.0- about 2.1.Such as second the refractive index of sublayer can include 2.0,2.01,2.02,2.03,2.04,2.05,
2.06,2.07,2.08,2.09,2.1 and all scopes between them and subrange.The refractive index of the second layer 524 can be
About 1.45- about 1.55.Such as the refractive index of the second layer 524 can include 1.45,1.46,1.47,1.48,1.49,1.50,1.51,
1.52,1.53,1.54,1.55 and all scopes between them and subrange.Described in more detail, the optics of following article
The first layer 520 of membrane structure 522 can have refractive index gradient.
Al is being utilized wherein in the second layer 5242O3A kind of embodiment in, nitrogen can be changed and oxygen concentration carrys out shape
Into Al2O3,AlOxNyAnd/or any of AlN or a variety of, to form the layer of optic film structure.
Figure 10 A totally show the optical property of the optic film structure 520 shown in Fig. 5.In the picture, the thickness in x-axis
Numerical value is represented in the thickness away from the optic film structure 520 on the direction of inorganic oxide substrate 110.Optical film is provided on the y axis
The refractive index value of structure 520, to show the variations in refractive index along the thickness of optic film structure.Figure 10 A picture is not examined
Consider inorganic oxide substrate 110 (or any other layer between inorganic oxide substrate 110 and optic film structure 520) or empty
The refractive index of gas (being arranged on any other layer on optic film structure 520).The sublayer 526 of inorganic oxide substrate 110 and first
Between interface represent that the interface between the first sublayer 526 and the second sublayer 528 is by the table of reference 910 by reference 900
Showing, the interface between the second sublayer 528 and the second layer 524 is represented by reference 920, and between the second layer 524 and air
Interface is represented by reference 930.As shown in Figure 10 A, the refractive index of the first sublayer 526 is along away from inorganic oxide substrate
Thickness increase of the direction at 110 (or the interfaces 900 of the sublayer of inorganic oxide substrate-the first 526) along the first sublayer 526.One
In kind or a variety of alternate embodiments, the refractive index of the first sublayer 526 changes with the change of the oxygen content in the first sublayer 526
Become.In addition, along most of thickness of the first sublayer 526, the refractive index of the first sublayer 526 is more than the refractive index of the second layer 524.
Along the integral thickness of the second sublayer, the refractive index of the second sublayer is more than the refractive index of the second layer 524.In Figure 10 A, the first He
The thickness of second sublayer 526,528 is shown as the thickness more than the second layer 524.In addition, the thickness of the first and second sublayers 526,528
Degree is shown as roughly equal；But in some embodiments, the thickness of the first and second sublayers 526, one of 528 can be more than
Another thickness in first and second sublayers.
Figure 10 B totally show the optical property of the alternate embodiments of the optic film structure shown in Fig. 5.Shown in Figure 10 B
Embodiment in, the refractive index of second-sublayer 528 is identical with the refractive index of the second layer 524.In one or more embodiments
In, the composition of the second sublayer 528 can be close or identical with least a portion of the second layer 524.In the picture shown in 10B, x-axis
On thickness value represent in the thickness away from the optic film structure 520 on the direction of inorganic oxide substrate 110.Carry on the y axis
For the refractive index value of optic film structure 520, to show the variations in refractive index along the thickness of optic film structure.Figure 10 B figure
Piece do not account for inorganic oxide substrate 110 (or between inorganic oxide substrate 110 and optic film structure 520 it is any its
Its layer) or air (or any other layer being arranged on optic film structure 520) refractive index.The He of inorganic oxide substrate 110
Interface between first sublayer 526 represents by reference 1000, the interface between the first sublayer 526 and the second sublayer 528 by
Reference 1010 represents that the interface between the second sublayer 528 and the second layer 524 is represented by reference 1020, and the second layer
Interface between 524 and air is represented by reference 1030.As shown in Figure 10 B, the refractive index of the first sublayer 526 is along remote
The direction of inorganic oxide substrate 110 (or the interface 900 of the sublayer of inorganic oxide substrate-the first 526) is along the first sublayer 526
Thickness increase.In one or more alternate embodiments, the refractive index of the first sublayer 526 is with the oxygen in the first sublayer 526
The change of content and change.In addition, at least a portion of the thickness along the first sublayer 526, the refractive index of the first sublayer 526 is small
In the refractive index of the second layer 524.Along the integral thickness of the second sublayer, the refractive index of the second sublayer and the refraction of the second layer 524
Rate is identical.In fig. 1 ob, the thickness of the first and second sublayers 526,528 is shown as the thickness more than the second layer 524；But such as
It is in need, the thickness of the first sublayer 526, the second sublayer 528 and the second layer 524 can relative to each other for it is equal or can it is thicker or
It is thinner, so as to provide required scratch resistance and optical property.In addition, the thickness of the first and second sublayers 526,528 is shown as
It is roughly equal；But in some embodiments, the thickness of the first and second sublayers 526, one of 528 can be more than first and the
Another thickness in two sublayers.
In the embodiment shown in Figure 4 and 5, the first layer 422,522 of optic film structure can have refractive index gradient.Folding
The rate gradient of penetrating can relate to oxygen and/or nitrogen content gradient in first layer 422,522, or can be by the composition in first layer 422,522
Gradient produces.First layer 222,322 shown in Fig. 2 and 3 can also have refractive index gradient.In this embodiment, optical film
The refractive index of the first layer of structure can increase along the direction away from inorganic oxide substrate 110 along thickness t.Such as refraction
Rate gradient can be about 1.45- about 2.2, or be specifically about 1.7- about 2.1.In the embodiment using oxygen content gradient,
Adjustable oxygen content optimizes the optical property along visible spectrum.Similarly, in the embodiment using nitrogen content gradient,
Adjustable nitrogen content optimizes the optical property along visible spectrum.
In one or more embodiments, first layer 222,322,422,522 is not siliceous or without aluminium.A kind of or more
In kind embodiment, first layer 222,322,422,522 includes AlN or Si3N4, but in first layer 222,322,422,
AlN or Si in 5223N4Oxide is set between inorganic oxide substrate 110.It is optical to adjust that the oxide can be selected
Matter, so as to which about 85% or bigger average transparency is presented in product on visible spectrum, as described elsewhere herein.In one kind
Or in numerous embodiments, oxide can be selected to adjust optical property, the total reflection presented so as to product on visible spectrum
Rate is equal to or less than the total reflectivity of the inorganic oxide substrate 110 without optic film structure as described herein.A kind of or more
In kind embodiment, oxide can be selected to adjust optical property, so as to which product is in (L, a*,b*) color is presented in colorimetric system
Transparency or reflectivity, it is less than about 2 so as to the color coordinates distance of distance reference point, as described elsewhere herein.
In one or more embodiments, optic film structure as described herein not nanostructure-containing or that deliberately adds receive
Rice structure, such as particle.The nanostructured deliberately added is the property for this nanostructured (such as in order to increase optics
The surface area of membrane structure or random layer in the structure shown here, in order to provide anti-dazzle property etc.) and it is intentionally introduced into optic film structure
Particle.In one or more embodiments, optic film structure as described herein without porous layer or has what is deliberately added
The layer of porosity.The porosity deliberately added includes processing optic film structure to provide or increase porosity or will form hole
Material is incorporated into optic film structure to provide or increase porosity.In one or more embodiments, the second layer 224,
324,424,524 exclude aluminium or aluminum ox nitride.
In one or more embodiments, optic film structure as described herein can include modifying agent to strengthen or suppress one
Kind or a variety of properties.In one or more embodiments, modifying agent can be combined into optic film structure to strengthen light
Learn the electrical conductivity of membrane structure.In this embodiment, Mg and/or Ca modifications or doping optical membrane structure can be used, so as to control
Electrical conductivity.Other modifying agent dopant such as Si and/or Ge can be combined into optic film structure as described herein, it is specific next
Say, be combined into the layer of the optic film structure comprising AlN.In one or more embodiments, using Si and/or Ge modifying agent
Or dopant causes refractive index to be controlled, and the oxygen or nitrogen content to given layer of optic film structure as described herein are not changed.
In other words, Si and/or Ge are used so that the refractive index to given layer within optic film structure is controlled, and need not change oxygen
Or nitrogen content.In addition, when it is a small amount of in use, Si can also REINFORCED Al N hardness (that is, provide AlNxSiyWherein y<0.1, and x+y
=1).If it is desired, boron can also form alloy with any materials as described herein.Such as AlN can form alloy to provide with boron
AlxByN, wherein x+y=1.It can be provided with reference to a small amount of boron for the specific layer within optic film structure or whole optical film structure
Improved lubricity.It can also be provided with reference to boron for the specific layer within optic film structure or whole optical film structure increased hard
Degree.The layer of optic film structure as described herein comprising nitrogen or nitride optionally includes carbon modifying agent or dopant.One
In kind or numerous embodiments, carbon modifying agent or dopant can use as alloy, so as to form carbon within optic film structure
Compound.Or optic film structure can be free of modifying agent or dopant or without the modifying agent or dopant deliberately added.
In one or more alternate embodiments, the modifying agent comprising hexagonal AlN or dopant can be combined into optics
Membrane structure, so as to improve the optical property of optic film structure.For example, hexagonal AlN can be combined into optic film structure, so as to increase
Add the refractive index of one or more layers of optic film structure.The layer of modified or doping optic film structure can include by this way
AlN,Si3N4,SiOxNy,SiuAlvOxNy, AlxSiyN or AlOxNy。
Optionally, hexagonal AlN can will be included, the modifying agent of Ag, Cr and/or other thick atoms is combined into optic film structure,
So as to improve the engineering properties of optic film structure.Specifically, can be by the way that hexagonal AlN, Ag, Cr and/or other thick atoms will be included
Modifying agent be combined into optic film structure, the stress come in management and control optic film structure.Although being not intended to be limited to theory, use
Some atom doped AlN, Si3N4,SiOxNy,SiuAlvOxNy,AlxSiyN or AlOxNyLayer may be such that film relaxation and with smaller
Stress.When exposed to force (such as single incident scraping), loose film is with tending not to sheet type separated, and this prevents to scrape damage simultaneously
It is also prevented from optical damage.The example of atom includes silver-colored (Ag), yttrium (Y), indium (In) and tin (Sn), and the cycle of the periodic table of elements the 5th
Other elements.In addition, also relaxing effect can be provided for optic film structure using phosphorus as dopant.Loose film is also to passing through
The drawing separation that the power occurred in the sliding contact event for causing to scrape is carried out is resistant.Therefore, some atoms are included
Into optic film structure so that film has required hardness, and without unfavorable stretching or compression.So, it is comprising some atoms
The optical property for adjusting optic film structure provides the extra free degree.
In one or more embodiments, hexagonal AlN modifying agent can be combined into optic film structure, to assign optics
Membrane structure lubricity.Hexagonal AlN can have the laminated structure similar to graphene.
In one or more embodiments, the coefficient of friction of optic film structure is smaller than including AlN, Si3N4,SiOxNy,
SiuAlvOxNy,AlxSiyN or AlOxNyBut hexagonal AlN modifying agent is not combined into other optic film structures of optic film structure
Coefficient of friction.Such as when using carbonization silicon ball to surface measurement, include AlN, Si3N4,SiOxNy,SiuAlvOxNy,
AlxSiyN or AlOxNyAbout 0.3 is smaller than with the coefficient of friction for the optic film structure for combining hexagonal AlN modifying agent.A kind of or
In numerous embodiments, coefficient of friction can be about 0.28 or smaller, about 0.26 or smaller, about 0.24 or smaller, about 0.22 or more
It is small, about 0.20 or smaller, about 0.18 or smaller, about 0.16 or smaller, about 0.14 or smaller, about 0.12 or smaller or about 0.1 or
It is smaller.
In one or more embodiments, modifying agent can be combined into comprising AlN, Si3N4,SiOxNy,
SiuAlvOxNy,AlxSiyN or AlOxNyOptic film structure layer in.Such as in the embodiment shown in figure 2, can be by modification
Agent is combined into comprising AlN or AlOxNyThe second sublayer 226 in.In the embodiment shown in Fig. 3, the first sublayer 326 and/
Or the 3rd sublayer 330 can combine modifying agent.In the embodiment shown in Fig. 4, first layer 422 can combine modifying agent.In Fig. 5 institutes
In the embodiment shown, the first sublayer 526 or the second sublayer 528 can combine modifying agent.
In one or more embodiments, modifying agent comprising fluorine can be combined into the second layer 224 as described herein,
324,424,524.In this embodiment, fluorine richness agent reduces the coefficient of friction of the second layer and gained optic film structure.Can
Fluorine richness agent is combined into other layers of optic film structure.In one or more embodiments, as described herein
Two layers include SiO2With the modifying agent containing fluorine.
In one or more embodiments, optic film structure as described herein excludes infrared reflecting layer or material.Optics
Membrane structure can also exclude layer or material with special regulation to the optical property of region of ultra-red.
As shown in Figure 1, inorganic oxide substrate 110 includes opposite minor surface 116,118.Implement in one or more
In mode, product 100 can include the film (not shown) of parcel, and it may be provided at opposite minor surface 116,118 and/or opposite
Major surfaces 112,114 on.In this embodiment, the film of parcel may be provided at inorganic oxide substrate 110 and optics
Between membrane structure 120,220,320,420,520.Or the film of parcel can form the whole of first layer 222,322,422,522
An or part.In a specific embodiment, the film of parcel can form all or part of of the first sublayer 226,326,526.Bag
The film wrapped up in can include Al2O3.The film of parcel can provide for the first sublayer 226,326,526 as described herein and first layer 424
Nucleating layer.Nucleating layer can influence the original of the atom of several atomic layers of the beginning of the first sublayer 226,326,526 or first layer 424
(interface i.e. between the film of the first sublayer 226,326,526 or first layer 424 and parcel is apart less than with nucleating layer for son arrangement
10nm)。
Product as described herein can include the extra film or layer being arranged on above the product.Such as product can be included and subtracted
Reflectance coating and/or passivating film.Exemplary antireflective coating can include simple layer or multiple layers (such as 4 tunics, 6 tunics etc.).When making
During with antireflective coating with multiple layers, these layers can include different refractive indexes and can include with high index of refraction (H) and low
The layer of refractive index (L), wherein " height " and " low " be relative to each other for and the known range that is antireflective coating.This can be set
A little layers, so as to high and low-index layer alternating.In one or more embodiments, can be in inorganic oxide substrate 110 and this
Intermediate layer is set between optic film structure described in text.In a specific embodiment, intermediate layer can include film or organic material,
The layer of inorganic material or its combination, the average flexural strength for maintenance goods.Intermediate layer can be several layers of complex, and this is several
Individual layer can have the composition being same to each other or different to each other.In one or more embodiments, intermediate layer includes polymer.Show
Example property polymer includes polyimides, polysiloxanes, polyether sulfone, polysulfones, poly- ethylether ketone, Parylene, polytetrafluoroethylene (PTFE)
Deng.Intermediate layer can also include diamond-like-carbon.Intermediate layer can have the crackle bridge joint for preventing to be formed in optic film structure to enter
Average failure strain, fracture toughness or the modulus properties of inorganic oxide substrate.In one or more embodiments, intermediate layer
The first sublayer of optic film structure as described herein can be formed.In this embodiment, the first sublayer comprising intermediate layer
Thickness can be about 300nm.It should be understood that the thickness of other layers of optic film structure can be more than 300nm, so as to which optic film structure is whole
Body has thickness as described elsewhere herein.When intermediate layer as independent layer between optic film structure or as optics
When a part for membrane structure is to include intermediate layer, optic film structure (and/or random layer among the structure) can be adjusted
To change the optical property of structure.
Following methods can be used to be arranged in inorganic oxide substrate 110 in optic film structure as described herein：Vacuum is sunk
Product technology, such as chemical vapor deposition (for example, plasma enhanced chemical vapor deposition), physical vapour deposition (PVD) is (for example, reaction
Property or non-reacted sputtering or laser ablation), thermal evaporation or electron beam evaporation and/or ald.It can change for setting
The processing conditions of optic film structure as described herein, come adjust the one of the engineering properties of optic film structure or optic film structure or
The engineering properties of multiple specific layers.Such as in one or more embodiments, depositing optical films knot at an elevated pressure
Structure, to reduce the stress within optic film structure.The pressure of exemplary elevated press packet millitorr containing about 0.5 millitorr-about 50.
In one or more embodiments, elevated press packet contains 10 millitorrs.In one or more embodiments, set at elevated pressures
Put the layer of the optic film structure comprising AlN.In a specific embodiment, other layers of optic film structure are for example not comprising AlN
Those layers can set at low pressures.The example of low-pressure includes the pressure of the millitorr of about 2 millitorrs-about 20.
The second aspect of the present invention is related to the method to form product as described herein.In one or more embodiments,
Methods described, which includes, provides inorganic oxide substrate, and it can be the glass of the reinforcing with opposite major surfaces as described herein
Glass base material, the glass baseplate of nonreinforcement, the glass-ceramic substrates of reinforcing or the glass-ceramic substrates of nonreinforcement, and it is inorganic at this
One of opposite major surfaces of oxide base material are upper to set optic film structure.In one or more embodiments, about 2
Under the pressure of the millitorr of millitorr-about 20, optic film structure is arranged in inorganic oxide substrate, so as to provide stress ratio relatively low
The lower optic film structure of the optic film structure that is deposited under pressure.In one or more embodiments, in about 3 millitorrs
Optic film structure is set under pressure.Available pressure alterable.Note that these is example and their accurate numerical value
It can be changed according to reactor used, reactor processing (such as reactor shape, size, carrier gas, flux etc.).
In one or more embodiments, optic film structure can be arranged on by inorganic oxide by evaporating deposition technique
On base material.Exemplary hollow deposition technique includes chemical vapor deposition, plasma enhanced chemical vapor deposition, and physical vapor is sunk
Product such as sputtering, thermal evaporation and ald.
In one or more embodiments, this method includes the one or more properties for changing optic film structure.This one
Kind or a variety of properties can include the anti-of electrical conductivity, lubricity, stress, refractive index, hardness, thickness, sedimentation rate and film and environment
Ying Xing, and combinations thereof.One or more in change electric conductivity, lubricity, stress and refractive index properties can include will be as herein
Described one or more modifying agent are combined into optic film structure.In one or more embodiments, this method, which includes, increases
Add the electrical conductivity of optic film structure.In a specific embodiment, increase optic film structure electrical conductivity include use can include Mg,
Ca or its combination modifying agent or dopant doping optical membrane structure.It can be included and increased according to the method for one or more embodiments
Add the lubricity of optic film structure.In one or more embodiments, the lubricity for increasing optic film structure includes general
BN is combined into optic film structure.In one or more embodiments, this method includes the stress reduced in optic film structure.
In this embodiment, reduction stress includes is combined into optical film knot by one or more in BN, Ag, Cr or its combination
Structure.
In one or more embodiments, this method includes and introduces oxygen into optic film structure.Optics can be changed by introducing oxygen
The refractive index of membrane structure.In one or more embodiments, this method, which can be included in optic film structure, builds oxygen content ladder
Degree, as described elsewhere herein.
Embodiment
It will be further elucidated by the following examples the different embodiments of the present invention.
It will be apparent to those skilled in the art can be in feelings without departing from the spirit and scope of the present invention
Various modifications and changes are carried out to the present invention under condition.
Embodiment 1-8
In the following embodiments, 3 layers of optic film structure are devised, and use different model evaluations sample in visible ray
Transparency in spectrum.Each layer of refractive index and extinction coefficient in three layers of optic film structure are characterized using ellipsometry.Will
Each layer of refractive index and extinction coefficient information is used for known modeling tool (for example, film design code), to determine in reality
Apply the optics behavior of the optic film structure described in a 1-8.Above-mentioned sign and modeling can be with optic film structures as described herein
Two layersth, four layers or other layers construction be used together.
In embodiment 1-8, measured and used refractive index and extinction coefficient information come from optic film structure, the light
Learn membrane structure and carry out shape using the ion beam sputtering process on the glass baseplate for the reinforcing in width and length dimension being about 2 " × 2 "
Into.The glass baseplate includes alkaline Boroalumino silicate glasses, and its composition includes about 65 moles of %SiO2, about 14 moles of %Al2O3；
About 5 moles of %B2O3；About 14 moles of %Na2O；About 2.5 moles of %MgO and about 0.1 mole of %SnO2.Glass baseplate be reinforced with
At least about 700MPa CS and at least about 40 μm of DOL is presented.By by glass baseplate in the melting that temperature is about 400-430 DEG C
About 4- is submerged in salt bath about 8 hours, to form the CS and DOL.The thickness of each layer of optic film structure is controlled by sedimentation time
System.Depositing temperature remains about 200 DEG C, and pressure remains 6.7x10-6Support.In argon gas that flow is about 75sccm, about 4kW
In the presence of D/C power, each layer of optic film structure is sputtered (for example, Ge targets are used for forming the oxygen comprising germanium from appropriate target
Compound, Si targets are used for forming siliceous oxide or Al targets are used for forming the oxide containing aluminium, nitride or nitrogen oxides).Make
With the mixture of oxygen (flow is about 2sccm), nitrogen (flow is about 50sccm) and argon gas (flow is about 25sccm) gas,
Ion beam is produced under about 180W- about 800W power.Such as formation Al2O3When, form ion under about 600W power
Beam, as formation AlOxNyWhen, ion beam is formed under about 180W power, and work as and form SiO2When, the shape under about 800W power
Into ion beam.Al is formed with the speed of about 3 angstroms per seconds2O3, AlO is formed with the speed of about 1.6 angstroms per secondsxNyWith with about 5 angstroms per seconds
Speed forms SiO2。
In known structure, when viewing angle changes to oblique incidence from normal incidence (that is, 0 degree), have minimum anti-
The design for penetrating rate still shows reflectivity color point change.Therefore, low reflectivity regions (and needing not to be minimum reflectivity regions)
(that is, low reflectivity regions are closer to (a for color with reduction*,b*) origin), this passes through two impedance-matching layers of design
Thickness and dispersion (dispersion) change to realize.
In embodiment 1, impedance-matching layer of optic film structure includes Al2O3And SiO2Layer, it rolls over around with height
Penetrate layer (such as the AlO of rate and higher hardnessxNy, wherein x >=0).Specifically, in embodiment 1, preparing has optical film knot
The sample of structure, the optic film structure include the first sublayer Al2O3, the second sublayer AlOxNyWith second layer SiO2, and use elliptical light
Degree method measures each layer of refractive index and extinction coefficient data.As described above, based on the refractive index and extinction coefficient data surveyed,
Change Al using modeling2O3And SiO2The thickness of layer.AlOxNyThe thickness of layer is constant.For SiO2And Al2O3Each thickness of layer
Degree, all predict the L of the sample according to embodiment 1*a*b*Color coordinates.Figure 11 shows the optic film structure according to embodiment 1 with saturating
The contour map of the color characteristics of rate expression is penetrated, wherein condition used is a*It is zero and b*It is zero.In addition, (a*,b*) set in space
The distance of the performance distance origin of meter is formed close to real agonic, white (or colourless) transparent measurement.
For the contour map shown in Figure 11, AlOxNyThickness is held constant at 1850nm, and SiO2And Al2O3The thickness of layer
Degree changes to 160nm from 0 respectively and changes to 800nm from 0, and this is completed using modeling as described above.Wrapped using fitting
The refractive index of layer containing these three materials and the Dispersion Function (Dispersion functions) of the experiment measurement of extinction coefficient.
Contour map shown in Figure 11 is restricted to the contour close to zero, is related to low color solution (a so as to provide*,
b*) ≈ (0,0) is to design parameter (that is, SiO2Layer and Al2O3Thickness degree) sensitiveness data.For clarity, inhibit other
Contour is horizontal.
As a result contour (the wherein a of full lines most thin wherein is shown*=0.0) and most thick dashed line form it is contour
Line (wherein b*=0.0), consistent solution be present in the region intersected or almost intersected.By comprising with Figure 11 this
The SiO of the thickness of a little intersections2,Al2O3, and AlOxNyLayer, it will thus provide there is the optic film structure of water white transparency degree.This light
Learn membrane structure and be shown in Table 1.
Table 1：The optic film structure with water white transparency degree from Figure 11.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 1 | 40nm | 1850nm | 500nm |
| Optic film structure 2 | 52nm | 1850nm | 440nm |
| Optic film structure 3 | 62nm | 1850nm | 450nm |
| Optic film structure 4 | 30nm | 1850nm | 350nm |
| Optic film structure 5 | 75nm | 1850nm | 330nm |
| Optic film structure 6 | 35nm | 1850nm | 160nm |
In example 2, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 2000nm.For SiO2And Al2O3The thickness of each simulation of layer, all predict the L of the sample according to embodiment 2*a*b*
Color coordinates.Relative to embodiment 1, AlOxNyThe thickness of layer increases to 2000nm, so as to show contour to AlOxNyThe thickness of layer
The dependence of degree.Figure 12 is the optic film structure color characteristics contour map represented with transmissivity according to embodiment 2.
By the SiO for including the thickness with these intersections in Figure 122,Al2O3, and AlOxNyLayer, it will thus provide tool
There is the optic film structure of colourless transparency.This optic film structure is shown in Table 2.
Table 2：The optic film structure with water white transparency degree from Figure 12.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 7 | 43nm | 2000nm | 500nm |
| Optic film structure 8 | 67nm | 2000nm | 490nm |
| Optic film structure 9 | 62nm | 2000nm | 450nm |
| Optic film structure 10 | 35nm | 2000nm | 350nm |
| Optic film structure 11 | 63nm | 2000nm | 300nm |
| Optic film structure 12 | 75nm | 2000nm | 380nm |
In embodiment 3, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 2250nm.Figure 13 is the contour map of the optic film structure color characteristics represented according to embodiment 3 with transmissivity, wherein
AlOxNyThe constant thickness of layer is 2250nm.
By the SiO for including the thickness with these intersections in Figure 132,Al2O3, and AlOxNyLayer, it will thus provide tool
There is the optic film structure of colourless transparency.This optic film structure is shown in Table 3.
Table 3：The optic film structure with water white transparency degree from Figure 13.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 13 | 48nm | 2250nm | 495nm |
| Optic film structure 14 | 65nm | 2250nm | 490nm |
| Optic film structure 15 | 60nm | 2250nm | 310nm |
| Optic film structure 16 | 37nm | 2250nm | 350nm |
| Optic film structure 17 | 72nm | 2250nm | 320nm |
In example 4, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 2500nm.Figure 14 is the contour map of the optic film structure color characteristics represented according to embodiment 4 with transmissivity, wherein
AlOxNyThe constant thickness of layer is 2500nm.
By the SiO for including the thickness with these intersections in Figure 142,Al2O3, and AlOxNyLayer, it will thus provide tool
There is the optic film structure of colourless transparency.This optic film structure is shown in Table 4.
Table 4：The optic film structure with water white transparency degree from Figure 14.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 18 | 53nm | 2500nm | 490nm |
| Optic film structure 19 | 60nm | 2500nm | 490nm |
| Optic film structure 20 | 38nm | 2500nm | 240nm |
| Optic film structure 21 | 68nm | 2500nm | 325nm |
In embodiment 5, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 2750nm.Figure 15 is the contour map of the optic film structure color characteristics represented according to embodiment 5 with transmissivity, wherein
AlOxNyThe constant thickness of layer is 2750nm.
By the SiO for including the thickness with these intersections in Figure 152,Al2O3, and AlOxNyLayer, it will thus provide tool
There is the optic film structure of colourless transparency.This optic film structure is shown in Table 5.
Table 5：The optic film structure with water white transparency degree from Figure 15.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 22 | 42nm | 2750nm | 340nm |
| Optic film structure 23 | 65nm | 2750nm | 330nm |
In embodiment 6, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 3000nm.Figure 16 is the contour map of the optic film structure color characteristics represented according to embodiment 6 with transmissivity, wherein
AlOxNyThe constant thickness of layer is 3000nm.
By the SiO for including the thickness with these intersections in Figure 162,Al2O3, and AlOxNyLayer, it will thus provide tool
There is the optic film structure of colourless transparency.This optic film structure is shown in Table 6.
Table 6：The optic film structure with water white transparency degree from Figure 16.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 24 | 42nm | 3000nm | 340nm |
| Optic film structure 25 | 61nm | 3000nm | 320nm |
In embodiment 7, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 3250nm.Figure 17 is the contour map of the optic film structure color characteristics represented according to embodiment 7 with transmissivity, wherein
AlOxNyThe constant thickness of layer is 3250nm.
By the SiO for including the thickness with the intersection in Figure 172,Al2O3, and AlOxNyLayer, it will thus provide have
The optic film structure of water white transparency degree.This optic film structure is shown in Table 7.
Table 7：The optic film structure with water white transparency degree from Figure 17.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 26 | 55nm | 3250nm | 330nm |
In embodiment 8, refractive index and extinction coefficient data measured in embodiment 1 are utilized.As described above, based on institute
The refractive index and extinction coefficient data of survey, change Al using modeling2O3And SiO2The thickness of layer；But AlOxNyThe thickness of layer is permanent
It is set to about 3500nm.Figure 18 is the contour map of the optic film structure color characteristics represented according to embodiment 8 with transmissivity, wherein
AlOxNyThe constant thickness of layer is 3250nm.
By the SiO for including the thickness with these intersections in Figure 182,Al2O3, and AlOxNyLayer, it will thus provide tool
There is the optic film structure close to colourless (but not being completely colorless) transparency.This optic film structure is shown in Table 8.
Table 7：The optic film structure having close to water white transparency degree from Figure 18.
| SiO2 | AlOxNy | Al2O3 | |
| Optic film structure 27 | 55nm | 3500nm | 340nm |
As shown in Figure 11-18, for AlOxNy layers (such as thickness about 3500nm) thicker in optic film structure, for
For the region of parameter space, the b in parameter space*No longer intersect (that is, b with zero in surface*Surface parameter space is no longer in b*
=zero-sum a*At=zero and a*Parameter space intersects).Therefore, during the thicker AlOxNy layers of use, adjust other layers (for example,
SiO2And Al2O3Layer) it is colourless or less close to the selection of water white transparency degree to obtain.
L*a*b*Particular color point (a in color space*,b*) apart from origin (0,0) distance by euclidean
(Euclidean) distance providesShown in Figure 19 A, 20A, 21A, 22A, 23A, 24A, 25A and 26A
Contour map shows the brightness L on the design space of same range according to embodiment 1-8 sample respectively*.Figure 19 B, 19C,
20B, 20C, 21B, 21C, 22B, 22C, 23B, 23C, 24B, 24C, 25B, 25C, 26B and 26C show embodiment 1-8 sample respectively
The collection of illustrative plates of product, wherein linear (Figure 19 B, 20B, 21B, 22B, 23B, 24B, 25B and 26B) and logarithm (Figure 19 C, 20C, 21C,
22C, 23C, 24C, 25C and 26C) under ratio, false color shows the numerical value d of the distance apart from origin with SiO2And Al2O3The change of thickness
Change.It will be mapped apart from the distance of color origin (limpid/white) relative to design parameter.
Figure 19 A, 20A, 21A, 22A, 23A, 24A, 25A and 26A show transparency or brightness, wherein bigger brightness represents
Bigger transparency.Figure 19 B, 19C, 20B, 20C, 21B, 21C, 22B, 22C, 23B, 23C, 24B, 24C, 25B, 25C, 26B and
Darker regions in 26C show in shown SiO2, Al2O3Under the thickness of AlOxNy layers, L*a*b*Apart from origin in color space
(0,0) distance is minimum.When comparison brightness and distance d, SiO can be obtained2、Al2O3With AlOxNy suitable thickness, so as to thoroughly
Lightness is maximized, while distance d (and color clarity) is to minimize.For example, in Figure 19 A and 19B, based on Figure 19 B,
SiO2Thickness degree is 35nm, Al2O3Thickness degree is that the optic film structure that 200nm and AlOxNy thickness degree is 1850nm can have nothing
Color transparency；But the brightness of this optic film structure can be 95%-96%.Similarly, SiO is selected2Thickness degree be 90nm,
Al2O3Thickness degree is that 100nm and AlOxNy thickness degree is the brightness that 1850nm can provide 99%；But this optic film structure
Distance d can be more than 2 or 3, thus without water white transparency degree.
With reference to figure 19C, 20C, 21C, 22C, 23C, 24C, 25C and 26C, the region of darker shows more insensitive to changing
Optic film structure design layer thickness.Therefore, these figures can be used to select tolerance matter to make the change of process and still obtain
The thickness of the layer of the optic film structure of required water white transparency degree.
Embodiment 9
Prepare embodiment 9 and comparative example 9A each sample respectively using sputtering method.Prepare in the following manner
Each sample：The base material that and length and width size used identical with embodiment 1-8 is all 50mm is provided.Embodiment 9 contains
There is SiuAlvOxNyLayer, wherein u, v, the thickness change of x and y along layer, contained with providing oxygen content gradient, silicone content gradient, aluminium
Measure gradient and nitrogen content gradient.Comparative example 9A includes AlN layers.As measured by profilometry, embodiment 9 includes
SiuAlvOxNyThe thickness of layer be about 260nm, and formed by using silicon and aluminium target and the sputter procedure of nitrogen and oxygen.
As measured by profilometry, the thickness of AlN layers (being free of gradient) is about 250nm.With the side of the layer similar to embodiment 9
Formula forms the comparative example 9A layer without gradient；But only utilize using aluminium target and only nitrogen.Form embodiment 9 and compare
Total sedimentation time of example 9A each layer is about 6 hours.
Figure 27, which is shown, includes SiuAlvOxNyThe layer of the embodiment 9 of gradient and the comparative example 9A without this gradient layer
Reflectivity %.Compared with the layer of the comparative example 9A without gradient, flat reflected light is presented in the layer of embodiment 9 on visible spectrum
Compose (or transmitted spectrum).In other words, relative to comparative example 9A uniform layer, the reflectivity % vibrations of the layer of embodiment 9
Amplitude reduces.As shown in figure 27, reflectivity of the layer of embodiment 9 on visible spectrum is that substantial constant or change are not more than
About 20%.In other words, the average reflectance of the layer of embodiment 9 is about 16%, and maximum (for example, 18%) and minimum value
(such as 14%) is differed with 16% average reflectance less than about 20%.In order to compare, the reflection of comparative example 9A AlN layers
Rate % display vibrations, 27% is up to about so as to which the reflectivity % on visible spectrum changes to from as little as about 8%.
Embodiment 10
Prepare embodiment 10 and comparative example 10A each sample respectively using sputtering method.Make in the following manner
Standby each sample：The base material that and length and width size used identical with embodiment 1-8 is all 50mm is provided.Embodiment 10 includes
One layer, the layer contain 121 and contain SiuAlvOxNySublayer, wherein u, v, the thickness change of x and y along layer, to provide oxygen
Concentration gradients, silicone content gradient, aluminium content gradient and nitrogen content gradient.By SiuAlvOxNy121 sublayers of layer form and arrive glass
On one side of base material.Form described layer in the following manner：It is about 20sccm in argon flow amount, nitrogen flow is
When 40sccm and oxygen flow are 2sccm, silicon target is sputtered first under the pressure of about 3 millitorrs.At least supplied at 3 minutes of beginning
4W RF power.After 3 minutes of beginning, D/C power is formed, with from aluminium target sputtered aluminum since 50W.Every 3 minutes of D/C power
Increase 20W, until reaching 300W.When D/C power increase, RF power, argon gas flow, nitrogen flow and oxygen flow are
Constant.After 300WDC power supplys are reached, RF power is reduced to 0W from 400W in continuous step, and D/C power continues
Increased power in a manner of increase 20W by every 3 minutes, until reaching 480W DC power.Then, in continuous step, with about
Oxygen flow is reduced to 0.25sccm oxygen by 0.2sccm increment from 2sccm, and the amount that last time reduces is 0.05sccm.
Oxygen flow is reduced to after 0.25sccm, and deposition process is further continued for carrying out 3 hours, and AlN is only formed in layer.In other words,
The sublayer formed when flow rate of the oxygen with 0.25sccm includes AlN.In whole deposition process, the flow of nitrogen and argon gas is
Constant, pressure is constant.In deposition process or between any change of flow, RF power or DC power, do not enter
Any cleaning of row.
Comparative example 10A includes single AlOxNyLayer.Embodiment 10 includes SiuAlvOxNyLayer thickness and comparative example 10A
AlOxNySimple layer thickness it is identical.Embodiment 10 is sputtered by using silicon and aluminium target and nitrogen and oxygen and carrys out shape
Into.Comparative example 10A (being free of gradient) is formed in a manner of similar to the layer of embodiment 10；But only utilize aluminium target and utilization
Oxygen and nitrogen.
Figure 28, which is shown, includes SiuAlvOxNyThe layer of the layer of the embodiment 10 of gradient and the comparative example 10A without this gradient
Transparency %.Compared with the comparative example 10A layer without gradient, the layer of embodiment 10 presents flat saturating on visible spectrum
Photopic spectrum.In other words, relative to comparative example 10A uniform layer, the amplitude of the transparency % vibrations of the layer of embodiment 10
Reduce.As shown in figure 28, transparency of the layer of embodiment 10 on visible spectrum is that substantial constant or change are not greater than about
4%.In order to compare, the reflectivity % display vibrations of comparative example 10A AlOxNy layers, so as to the transparency % on visible spectrum
Changed to from as little as about 78% and be up to about 93%.Scratch-resistant as described elsewhere herein is also presented in the gradient layer of embodiment 10
Property.
Although being not intended to be limited to theory, it is believed that when thickness linear reduction of the oxygen content along layer, light as described herein
The amplitude of the reflectivity % of membrane structure vibration is learned, and includes aluminium content, silicone content, nitrogen content and/or oxygen content gradient
The reflectivity % of layer (such as the sublayer 526 of first layer 422 and/or first and/or layer of embodiment 9 and embodiment 10) vibration
Amplitude can be reduced to be approximately zero.
Embodiment 11
In the following embodiments, the 3 layers of optic film structure set on the glass substrate are devised.According to embodiment 1-
8 identical modes, using the transparency of various model evaluation optic film structures and glass baseplate over the entire visual spectrum and instead
Penetrate ratio.Ellipsometry is reused to characterize each layer of refractive index and extinction coefficient in three layers of optic film structure.Will be each
The refractive index and extinction coefficient information of layer are used for known modeling tool (for example, film design code), to determine optical film knot
The optics behavior of structure and base material.
Using with identical base material used in embodiment 1-8, form optical film knot in a manner of with embodiment 1-8 identicals
Structure.
In embodiment 11, impedance-matching layer of optic film structure includes Al2O3And SiO2Layer, it rolls over around with height
Penetrate the layer of rate and higher hardness.Specifically, optic film structure includes the first sublayer Al2O3, the second sublayer AlOxNyAnd the second layer
SiO2.As described above, based on the refractive index and extinction coefficient data surveyed, change Al using modeling2O3And SiO2The thickness of layer.
AlOxNyThe constant thickness of layer is 2 microns.For SiO2And Al2O3Each thickness of layer, all predict the L of sample*a*b*Color is sat
Mark.
Figure 29 A show a of the optic film structure and base material according to embodiment 11*The contour map of reflectivity color characteristics.
In contour map, numerical value is zero to show that the reflectivity of optic film structure and substrate combination is free of color.Suitable for SiO2Layer and
Al2O3The thickness of layer is included along solid line R, a*=0.5 and dotted line R, a*The thickness of contour between=- 0.5, or at some
In the case of, comprising along two dotted line R, a*The thickness of contour between=0.As the SiO with these thickness2And Al2O3Layer with
2 μm of AlOxNyDuring layer combination, a of optical film and base material presentation*Numerical value is about -0.5 to about 0.5, this so that limit optical film and
The color coordinates and color coordinates (a of base material*=0, b*The distance between=0).For 0nm-500nm Al2O3Thickness, properly
SiO2The example of thickness degree includes about 0nm- about 60nm, and is used for Al2O3And/or SiO2The specific thickness of layer falls in solid line R, a*
=0.5 and dotted line R, a*Between=- 0.5.In one or more embodiments, for 0nm-500nm Al2O3Thickness, properly
SiO2The thickness of layer may also include about 0nm- about 150nm thickness；But using falling in solid line R, a*=0.5 and dotted line R, a*
The thickness of the thickness degree of wider range between=- 0.5 provides more flexibilities (that is, a small amount of change of thickness will not for manufacture
Significantly affect a*Numerical value).For this, 0nm-60nm SiO2The Al of thickness and 0nm-200nm2O3Thickness degree can be provided to optical film
The bigger tolerance of thickness change, while a that the optical film and substrate combination provided is presented*Numerical value is about -0.5 to about 0.5, face
Chromaticity coordinates is with minimum apart from color coordinates (a*=0, b*=0) distance.
Figure 29 B show a of the optic film structure and following base material according to embodiment 11*Reflectivity color characteristics it is contour
Line chart, and contour shows the difference between optic film structure and the combination of base material and naked base material (being free of optic film structure).
In contour map, the numerical value for the amount of mapping means the color coordinates of the combination of optic film structure and base material and naked base when being zero
The color coordinates of material is identical.As shown in fig. 29b, contour is changed to adapt to base material.Therefore, from those shown in Figure 29 A
Change solid line R, a*=0.5 and dotted line R, a*SiO between=- 0.52And Al2O3The thickness or in some cases of layer, two dotted lines
R,a*SiO between=- 0.52And Al2O3The thickness of layer.As the SiO with these thickness2And Al2O3Layer and 2 μm of AlOxNyLayer
During combination, a of the combination presentation of optical film and base material*Numerical value is about -0.5 to about 0.5, this so that limit optical film and base material group
The distance between color coordinates of the color coordinates of conjunction and naked base material (being free of optical film).For 0nm-500nm Al2O3Thickness,
Suitable SiO2The example of thickness degree includes about 0nm- about 60nm, and is used for Al2O3And/or SiO2The specific thickness of layer falls in reality
Line R, a*=0.5 and dotted line R, a*Between=- 0.5.In one or more embodiments, for 0nm-500nm Al2O3It is thick
Degree, suitable SiO2The thickness of layer may also include about 0nm- about 140nm thickness；But using falling in solid line R, a*=0.5 He
Dotted line R, a*The thickness of the thickness degree of wider range between=- 0.5 provides more flexibilities (that is, thickness is a small amount of for manufacture
Change is not significantly affected by a*Numerical value).For this, the SiO that thickness is about 0nm- about 60nm is used2Layer and thickness be about 0nm- about
200nm Al2O3Layer can change for optical film thickness provides bigger tolerance, while the optical film and substrate combination that provide are in
Existing a*Numerical value is about -0.5 to about 0.5.During with substrate combination, this SiO is used in optical film2And Al2O3Layer and 2 μ m-thicks
The product that provides of AlOxNy the layers color coordinates and the color coordinates (a that present*=0, b*=0) it is closer to the distance (such as<2).
Figure 29 C show the b of the optic film structure and base material according to embodiment 11*The contour map of reflectivity color characteristics.
In contour map, numerical value is zero to show that the combination of optic film structure and base material is free of color.Suitable for SiO2Layer and Al2O3Layer
Thickness is included along solid line R, b*=0.5 and dotted line R, b*The thickness of contour between=- 0.5, or in some cases, bag
Containing along two dotted line R, b*The thickness of contour between=- 0.5.As the SiO with these thickness2And Al2O3Layer with 2 μm
AlOxNyDuring layer combination, the b of optical film and substrate combination presentation*Numerical value is about -0.5 to about 0.5, and this and then limitation and color are sat
Mark (a*=0, b*=0) distance.For 0nm- about 500nm Al2O3Thickness degree, suitable SiO2The example of thickness degree includes about
0- about 40nm, or about 170nm- about 175nm, and Al2O3And SiO2The more specifically thickness of layer falls in solid line R, b*=0.5 and empty
Line R, b*Between=- 0.5.The SiO2 layers that usable thickness is about 175nm, and can provide with improved b*Reflectivity color
The combination of the optical film and base material of energy；But it can all cause b with the arbitrary deviation of the thickness*Numerical value change.
Figure 29 D show the b of the optic film structure and base material according to embodiment 11*The contour map of reflectivity color characteristics.
Contour in contour map shows the difference between optic film structure and the combination of base material and naked base material (being free of optic film structure)
It is different.In contour map, the numerical value for the amount of mapping means the color coordinates of the combination of optic film structure and base material when being zero
It is identical with the color coordinates of naked base material.As shown in Figure 29 D, contour is changed to adapt to base material.Therefore, from shown in Figure 29 C
Those modifications solid line R, b*=0.5 and dotted line R, b*SiO between=- 0.52And Al2O3The thickness or in some cases of layer,
Two dotted line R, b*SiO between=- 0.52And Al2O3The thickness of layer.As the SiO with these thickness2And Al2O3Layer with 2 μm
AlOxNyDuring layer combination, the b of the combination presentation of optical film and base material*Numerical value is about -0.5 to about 0.5, this so that limit optical film
The distance between color coordinates of the color coordinates of substrate combination and naked base material (being free of optical film).For 0nm- about 500nm
Al2O3Thickness degree, suitable SiO2The example of thickness degree includes about 0- about 30nm, or about 170nm- about 175nm, and Al2O3With
SiO2More specifically thickness fall in solid line R, b*=0.5 and dotted line R, b*Between=- 0.5.Compared with Figure 29 C, in Figure 29 D
Al2O3The thickness and thickness range of layer are not change significantly in.
Figure 29 E show SiO2And Al2O3The thickness of layer, in the SiO2And Al2O3Product under the thickness of layer (comprising optical film and
Base material) reflectivity color coordinates and color coordinates (a*=0, b*=0) distance is approximately less than 1, is approximately less than 0.5, is approximately less than 0.2
Be approximately less than 0.1.Figure 29 E show the SiO that when optical film there is thickness to be about 0nm- about 50nm2Layer and thickness be about 0nm- about
180nm Al2O3Layer, and Al2O3And/or SiO2The more specifically thickness of layer falls between solid line d=0.1 and dotted line d=1.0,
And when being combined with the AlOxNy layers of 2 μ m-thicks, the color coordinates represented with reflectivity and color coordinates (a that the optical film is presented*=
0,b*=0) distance is approximately less than 1.In another embodiment, thickness is about 0nm- about 50nm SiO2Layer, thickness be about 0nm- about
500nm Al2O3Required reflectivity color characteristics are also presented in layer, the combination of the AlOxNy layers of 2 μ m-thicks and glass baseplate.Another
In one embodiment, thickness is about 75nm- about 100nm SiO2Layer, the Al that thickness is about 250nm- about 500nm2O3Layer, 2 μ m-thicks
Required reflectivity color characteristics are also presented in the combination of AlOxNy layers and glass baseplate；But SiO2And Al2O3These thickness models of layer
Enclose lower to the tolerance of thickness change, find to improve the transparency of the combination of optical film and base material on some other thickness.
Figure 29 F show SiO2And Al2O3The thickness of layer, in the SiO2And Al2O3Layer thickness under product color coordinates with
The distance of the color coordinates of base material is approximately less than 1, is approximately less than 0.5, is approximately less than 0.2 and is approximately less than 0.1.Figure 29 F show to work as glass base
The SiO that material is about 0nm- about 30nm or 35nm with AlOxNy layers, thickness comprising 2 μ m-thicks2Layer and thickness are about 0nm- about 170nm
Al2O3Layer (and Al2O3And/or SiO2Layer more specifically thickness fall between solid line d=0.1 and dotted line d=1.0) optics
When film combines, the color coordinates represented with reflectivity of combination presentation and the color coordinates of base material of the glass baseplate and optical film
Distance be approximately less than 1.Another embodiment includes base material and optical film, and AlOxNy layers, the thickness that the optical film includes 2 μ m-thicks are about
30nm- about 40nm SiO2The Al that layer and thickness are about 260nm- about 290nm2O3Layer.Another embodiment includes base material and optics
Film, the SiO that AlOxNy layers, the thickness that the optical film includes 2 μ m-thicks are about 20nm- about 40nm2Layer and thickness be about 420nm- about
450nm Al2O3Layer.
Figure 30 A show a of the optic film structure and base material according to embodiment 11*The contour map of transparency color characteristics.
In the contour map, numerical value is zero to show that optic film structure and substrate combination are free of color.SiO2Layer and Al2O3Layer it is suitable
Thickness include along solid line T, a*=0.5 and dotted line T, a*The thickness of contour between=- 0.5 or in some cases,
Two dotted lines T, a*The thickness of contour between=- 0.5, when with 2 μm of AlO in optical filmxNyDuring layer combination, it will be provided
About -0.5 to about 0.5 a*Numerical value.As the SiO with these thickness2And Al2O3Layer and 2 μm of AlOxNyDuring layer combination, optical film
The a of presentation*Numerical value is about -0.5 to about 0.5, this so that limit the color coordinates and color coordinates (a of optical film and base material*=0,
b*The distance between=0).For 0nm- about 500nm Al2O3Thickness degree, suitable SiO2The example of thickness degree includes about 0- about
160nm, and Al2O3And SiO2More specifically thickness fall in solid line T, a*=0.5 and dotted line T, a*Between=- 0.5.It can not provide
Required a*The example of the thickness of transparency includes the SiO that thickness is about 65nm- about 105nm2Layer with thickness be about 10nm- about
120nm Al2O3Layer combination, thickness is about 20nm- about 140nm SiO2Layer and the Al that thickness is about 185nm- about 275nm2O3Layer
Combination, or the SiO that thickness is about 0nm- about 125nm2Layer and the Al that thickness is about 350nm- about 420nm2O3The combination of layer, because
It is these thickness ranges and assembly drop in two dotted lines T, a*Between=- 0.5.
Figure 30 B show a of the optic film structure and base material according to embodiment 11*The contour map of transparency color characteristics.
The contour shows the difference between optic film structure and the combination of base material and naked base material (being free of optic film structure).It is contour at this
In line chart, the numerical value for the amount of mapping means the color coordinates of the combination of optic film structure and base material and naked base material when being zero
Color coordinates is identical.As shown in figure 30b, contour is changed to adapt to base material.Therefore, from those modifications shown in Figure 30 A
Solid line T, a*=0.5 and dotted line T, a*SiO between=- 0.52And Al2O3The thickness or in some cases of layer, two dotted line T, a*
SiO between=- 0.52And Al2O3The thickness of layer.As the SiO with these thickness2And Al2O3Layer and 2 μm of AlOxNyLayer combination
When, a of optical film and base material presentation*Numerical value is about -0.5 to about 0.5, this so that limit the color coordinates of optical film and base material with
The distance between color coordinates of naked base material (being free of optical film).For 0nm- about 500nm Al2O3Thickness degree, suitable SiO2
The example of thickness degree includes about 0- about 160nm, and Al2O3And/or SiO2The more specifically thickness of layer falls in solid line T, a*=0.5
With dotted line T, a*Between=- 0.5.Required a can not be provided*The example of the thickness of transparency comprising thickness be about 65nm- about
105nm SiO2Layer and the Al that thickness is about 0nm- about 120nm2O3Layer combination, thickness is about 20nm- about 120nm SiO2Layer with
Thickness is about 190nm- about 275nm Al2O3The combination of layer, or the SiO that thickness is about 0nm- about 125nm2Layer and thickness are about
330nm- about 420nm Al2O3The combination of layer, because these thickness ranges and assembly drop are in two dotted line T, a*Between=- 0.5.
Figure 30 C show the b of the optic film structure and base material according to embodiment 11*The contour map of transparency color characteristics.
In the contour map, numerical value is zero to show that the combination of optic film structure and base material is free of color.Suitable for SiO2Layer and Al2O3Layer
Thickness include along solid line T, b*=0.5 and dotted line T, b*The thickness of contour between=- 0.5, or in some cases,
Comprising along two dotted line T, b*The thickness of contour between=- 0.5.As the SiO with these thickness2And Al2O3Layer with 2 μm
AlOxNyDuring layer combination, the b of the combination presentation of optical film and base material*Numerical value is about -0.5 to about 0.5, this so that limit optics
The color coordinates and color coordinates (a of membrane structure and base material*=0, b*The distance between=0).For 0nm- about 500nm Al2O3
Thickness degree, suitable SiO2The example of thickness degree includes about 0- about 90nm, and Al2O3And/or SiO2The more specifically thickness of layer falls
In solid line T, b*=0.5 and dotted line T, b*Between=- 0.5.Required b can not be provided*The example of the thickness of transparency includes thickness
It is about 20nm- about 80nm SiO2Layer and the Al that thickness is about 0nm- about 250nm2O3Layer combination, thickness be about 20nm- about
80nm SiO2Layer and the Al that thickness is about 260nm- about 500nm2O3The combination of layer, or the SiO that thickness is about 0nm- about 25nm2
Layer with thickness is about 80nm- about 150nm, about 220nm- about 290nm or about 380nm- about 440nm Al2O3The combination of layer, because
These thickness ranges and assembly drop are in two dotted line T, b*Between=- 0.5 or in two solid line T, b*Between=0.5.
Figure 30 D show the b of the optic film structure and base material according to embodiment 11*The contour map of reflectivity color characteristics.
The contour shows the difference between optic film structure and the combination of base material and naked base material (being free of optic film structure).It is contour at this
In line chart, the numerical value for the amount of mapping means the color coordinates of the combination of optic film structure and base material and naked base material when being zero
Color coordinates is identical.As shown in fig. 30d, contour is changed to adapt to base material.Therefore, from those modifications shown in Figure 30 C
Solid line T, b*=0.5 and dotted line T, b*SiO between=- 0.52And Al2O3The thickness or in some cases of layer, two dotted line T, b*
SiO between=- 0.52And Al2O3The thickness of layer.As the SiO with these thickness2And Al2O3Layer and 2 μm of AlOxNyLayer combination
When, the b of optical film presentation*Numerical value is about -0.5 to about 0.5, this so that limit the color coordinates of optical film and substrate combination with it is naked
The distance between color coordinates of base material (being free of optical film).For 0nm- about 500nm Al2O3Thickness degree, suitable SiO2Layer
The example of thickness includes about 0- about 40nm, about 70nm- about 100nm or about 160nm- about 175nm, and Al2O3And/or SiO2Layer
More specifically thickness falls in solid line T, b*=0.5 and dotted line T, b*Between=- 0.5.Required b can not be provided*The thickness of transparency
Example include thickness be about 0nm- about 80nm SiO2Layer and the Al that thickness is about 0nm- about 500nm2O3The combination of layer, thickness
It is about 80nm- about 170nm SiO2Layer and the Al that thickness is about 0nm- about 500nm2O3Layer combination, or thickness be about 0nm- about
25nm SiO2Layer and thickness are about 100nm- about 130nm, or about 230nm- about 290nm, or about 390nm- about 420nm Al2O3
The combination of layer, because some in these thickness ranges and combination fall in two dotted line T, b*Between=- 0.5 or in two solid line T, b*
Between=0.5.
Figure 30 E show SiO2And Al2O3The thickness of layer, in the SiO2And Al2O3About product (includes optical film under the thickness of layer
And base material) reflectivity color coordinates and color coordinates (a*=0, b*=0) distance is less than 1, is approximately less than 0.5, is approximately less than 0.2
Be approximately less than 0.1.Figure 30 E show a kind of optical film, wherein the considerably less SiO for meeting following condition be present2Layer and Al2O3Layer
In the thickness of any one, when in the SiO2Layer and Al2O3Combined in layer under the thickness of any one with the AlOxNy layers of 2 μ m-thicks
Shi Chengxian is with the color coordinates that transparency represents and color coordinates (a*=0, b*=0) distance is approximately more than 1.For example, work as optical film
With the SiO that thickness is about 0nm- about 50nm2The Al that layer and thickness are about 0nm- about 500nm2O3Layer (and Al2O3And/or SiO2Layer
More specifically thickness fall between solid line d=0.1 and dotted line d=1.0) and when being combined with the AlOxNy layers of 2 μ m-thicks, the optics
The color coordinates represented with transparency that film is presented and color coordinates (a*=0, b*=0) distance is approximately less than 1.In another implementation
In example, SiO2Thickness degree can be about 0nm- about 50nm and Al2O3Thickness degree can be about 0nm- about 220nm, and Al2O3And/or SiO2
The more specifically thickness of layer falls between solid line d=0.1 and dotted line d=1.0.In another embodiment, SiO2Thickness degree can be
About 60nm- about 100nm and Al2O3Thickness degree can be about 100nm- about 500nm, and Al2O3And/or SiO2The more specifically thickness of layer
Fall between solid line d=0.1 and dotted line d=1.0.
Figure 30 F show SiO2And Al2O3The thickness of layer, in the SiO2And Al2O3Layer thickness under product color coordinates with
The distance of the color coordinates of base material is approximately less than 1, is approximately less than 0.5, is approximately less than 0.2 and is approximately less than 0.1.Figure 30 F show when base material with
The SiO that AlOxNy layers, thickness comprising 2 μ m-thicks are about 0nm- about 50nm2The Al that layer and thickness are about 0nm- about 200nm2O3Layer
(and Al2O3And/or SiO2Layer more specifically thickness fall between solid line d=0.1 and dotted line d=1.0) combination of optical films
When, the color coordinates represented with transparency that the combination of the glass baseplate and optical film is presented and the color coordinates of naked base material away from
From being approximately less than 1.In another embodiment, SiO2Thickness degree can be about 70nm- about 100nm and Al2O3Thickness degree can be about 100nm-
About 500nm, and Al2O3And/or SiO2The more specifically thickness of layer falls between solid line d=0.1 and dotted line d=1.0.
In Figure 29 A-29F and 30A-30F, a is utilized*And b*For from -0.5 to 0.5 and d=0.1,0.2,0.5 and 1 etc.
High line illustrates different designs parameter, to obtain optical property as described herein.It is noted that depending on light source interested and/
Or (that is, some are observer found that a for observer's preference*,b*,a*And b*Combination larger change and bigger distance d be can
Receive), can be used has larger range of contour (for example, a*Or b*It is about -1 to about 1 or about -2 to about 2, or d=1.5,
2,2.5 etc.).
It will be apparent to those skilled in the art can be in the feelings without departing from scope and spirit of the present invention
Various modifications and changes are carried out to the present invention under condition.
Claims (20)
1. a kind of product, it includes：
Inorganic oxide substrate with opposite major surfaces；With
The optic film structure being arranged on the first major surfaces of the inorganic oxide substrate, the thickness of the optic film structure is about
For 1-20 microns, and include the one or more in following material：Siliceous oxide, siliceous nitrogen oxides, silicon nitride,
Aluminium nitride, the nitrogen oxides containing aluminium, oxide and silicon aluminium keto nitride containing aluminium；
85% or bigger average transparency is presented in wherein described product on visible spectrum, and following one kind or more is presented
Kind:
Have when normal incidence is watched transparency color coordinates in (L, a*,b*) color clarity in colorimetric system, so as to
The distance between the transparency color coordinates and reference point be less than about 2, and
Have when normal incidence is watched reflectivity color coordinates in (L, a*,b*) color reflective ratio in colorimetric system, so as to
The distance between the reflectivity color coordinates and reference point be less than about 2, and
Wherein the reference point includes color coordinates (a*=0, b*And at least one of the color coordinates of base material ,=0) and
Wherein, when reference point is the color coordinates of base material, With
Wherein, when reference point is color coordinates (a*=0, b*=0) when,
2. product as claimed in claim 1, it is characterised in that as measured by tieing up strange pressure head test by diamond problem about Bellco haemodialysis,
Optic film structure includes about 16GPa or bigger hardness.
3. product as claimed in claim 1, it is characterised in that the optic film structure includes siliceous oxide, siliceous
One in nitrogen oxides, silicon nitride, aluminium nitride, the nitrogen oxides containing aluminium, the oxide containing aluminium, silicon-aluminium-nitride-oxide or its combination
Kind.
4. product as claimed in claim 1, it is characterised in that the optic film structure includes at least two layers, wherein first layer
It is arranged between the inorganic oxide substrate and the second layer.
5. product as claimed in claim 4, it is characterised in that the first layer includes siliceous oxide, siliceous nitrogen oxygen
At least one of compound, silicon nitride, aluminium nitride, the nitrogen oxides containing aluminium, the oxide containing aluminium and silicon-aluminium-nitride-oxide, wherein
The second layer includes SiO2、GeO2And Al2O3At least one of.
6. product as claimed in claim 4, it is characterised in that the first layer includes Al2O3, AlN, AlOxNy or its combination.
7. product as claimed in claim 4, it is characterised in that the first layer contains Al2O3The first sublayer and comprising
AlN the second sublayer, and wherein the first sublayer is arranged between inorganic oxide substrate and the second sublayer.
8. product as claimed in claim 4, it is characterised in that the first layer contains AlOxNyThe first sublayer and bag
The second sublayer containing AlN, and wherein the first sublayer is arranged between inorganic oxide substrate and the second sublayer.
9. product as claimed in claim 4, it is characterised in that the first layer also includes SiO2。
10. product as claimed in claim 1, it is characterised in that the thickness of the optic film structure is 2 μm or bigger.
11. product as claimed in claim 1, it is characterised in that the optic film structure includes AlN, and wherein using modification
AlN is adulterated in agent, and the modifying agent includes the one or more in BN, Ag, Cr, Mg and Ca.
12. product as claimed in claim 1, it is characterised in that the inorganic oxide substrate includes crystal substrate or without fixed
Shape base material.
13. product as claimed in claim 1, it is characterised in that also include and be arranged on the optic film structure and the inorganic oxide
Intermediate layer between thing base material.
14. a kind of product, it includes：
Inorganic oxide substrate with opposite major surfaces and base material hardness；
The optic film structure being arranged on the first major surfaces of the inorganic oxide substrate, the optic film structure include first
The second layer of layer and setting on the first layer, the first layer include the nitride containing aluminium, the nitrogen oxides containing aluminium, the oxidation containing aluminium
Thing or its combination；
Wherein described optic film structure includes the hardness more than the base material hardness；And
85% or bigger average transparency is presented in wherein described product on visible spectrum, and following one kind or more is presented
Kind:
Have when normal incidence is watched transparency color coordinates in (L, a*,b*) color clarity in colorimetric system, so as to
The distance between the transparency color coordinates and reference point be less than about 2, and
Have when normal incidence is watched reflectivity color coordinates in (L, a*,b*) color reflective ratio in colorimetric system, so as to
The distance between the reflectivity color coordinates and reference point be less than about 2, and
Wherein the reference point includes color coordinates (a*=0, b*And at least one of the color coordinates of base material ,=0) and
Wherein, when reference point is the color coordinates of base material, With
Wherein, when reference point is color coordinates (a*=0, b*=0) when,
15. product as claimed in claim 14, it is characterised in that the first layer includes including the first sublayer, the second sublayer
With the 3rd sublayer, wherein the second sublayer is arranged between the first sublayer and the 3rd sublayer, and wherein the first sublayer and the 3rd sublayer
Comprising AlN, the second sublayer includes SiO2。
16. product as claimed in claim 14, it is characterised in that the second layer includes SiO2,GeO2,Al2O3, and its group
Close.
17. product as claimed in claim 14, it is characterised in that the optic film structure also include selected from BN, Ag, Cr and its
The modifying agent of combination.
18. product as claimed in claim 17, it is characterised in that when close to carbonization silicon ball to surface measurement when, the optics
The coefficient of friction that membrane structure is presented is less than 0.3.
19. a kind of method for forming base material, this method include：
Inorganic oxide substrate is provided, it has opposite major surfaces and comprising amorphous base material or crystal substrate；With
Under the pressure of the millitorr of about 0.5 millitorr-about 10, low answer is set on the first major surfaces of the inorganic oxide substrate
Power optic film structure, it is 16GPa or bigger first layer and sets on the first layer wherein the optic film structure includes hardness
The second layer.
20. method as claimed in claim 19, it is characterised in that methods described also includes following at least one：Increase institute
The electrical conductivity of optic film structure is stated, increases the lubricity of the optic film structure, and reduce the stress in the optic film structure.
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| US201361820407P | 2013-05-07 | 2013-05-07 | |
| US61/820,407 | 2013-05-07 | ||
| US201361877568P | 2013-09-13 | 2013-09-13 | |
| US61/877,568 | 2013-09-13 | ||
| CN201480038941.2A CN105377782B (en) | 2013-05-07 | 2014-05-06 | Has the product of the scratch-resistant of optical property with a grain of salt |
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| CN202210101797.9A Active CN114349366B (en) | 2013-05-07 | 2014-05-06 | Scratch resistant articles with retained optical properties |
| CN201480038941.2A Active CN105377782B (en) | 2013-05-07 | 2014-05-06 | Has the product of the scratch-resistant of optical property with a grain of salt |
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| CN201480038941.2A Active CN105377782B (en) | 2013-05-07 | 2014-05-06 | Has the product of the scratch-resistant of optical property with a grain of salt |
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| EP (1) | EP2994435B1 (en) |
| JP (1) | JP6052839B2 (en) |
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| CN105377782B (en) | 2017-06-13 |
| TW201447350A (en) | 2014-12-16 |
| CN105377782A (en) | 2016-03-02 |
| CN107352815B9 (en) | 2022-04-01 |
| US20150376057A1 (en) | 2015-12-31 |
| US20230303432A1 (en) | 2023-09-28 |
| TWI533017B (en) | 2016-05-11 |
| US20140335335A1 (en) | 2014-11-13 |
| CN114349366A (en) | 2022-04-15 |
| CN107352815B (en) | 2022-02-18 |
| KR20160003286A (en) | 2016-01-08 |
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| US9110230B2 (en) | 2015-08-18 |
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| WO2014182640A1 (en) | 2014-11-13 |
| JP2016524581A (en) | 2016-08-18 |
| KR101633245B1 (en) | 2016-06-23 |
| US11667565B2 (en) | 2023-06-06 |
| CN114349366B (en) | 2023-09-01 |
| JP6052839B2 (en) | 2016-12-27 |
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Correction item: Claims Correct: Claims submitted on January 29, 2022 False: Claims submitted on November 4, 2021 Number: 07-02 Page: full text Volume: 38 |